Novel modification of polybut‐1‐ene using auto‐oxidation controlled by addition of limonene monomer

Free radical graft polymerization has been used as a modification method to incorporate functional groups into polyolefins using a melt‐mixing process. The presence of oxygen simultaneously brings about auto‐oxidation during the polymerization. Although functional groups such as ketones are easily incorporated into polyolefin chains by auto‐oxidation, the method is rarely employed because of the difficulty of handling. In the study reported here, a novel modification of polybut‐1‐ene (PB) was performed using auto‐oxidation controlled by the addition of limonene monomer. The modified PB samples were prepared using 2,2′‐azobis(2‐methylpropionitrile), benzyl peroxide, tert‐butyl peroxide (TBPO) and Nd₂O₃/dicumyl peroxide (DCP) radical initiators in air. It was found that excessive auto‐oxidation was suppressed by the presence of the limonene, and that the greatest numbers of grafted groups were contained in the modified PB samples prepared using TBPO and Nd₂O₃/DCP. The samples obtained showed slower crystallization behavior and slower crystal–crystal transformation rates, respectively. In addition, the modified PB sample prepared using Nd₂O₃/DCP showed less ductile behavior than that prepared using TBPO because of a much slower transformation rate. Copyright © 2009 Society of Chemical Industry     

Preparation of polybutene‐1/multiwall carbon nanotube composite by oxidation and limonene radical grafting and its characterization

In this study, a novel preparation of a polybutene‐1 (PB) and multiwall carbon nanotube (MWNT) composite was achieved by a combination of PB autooxidation and a radical grafting reaction using an Nd₂O₃/dicumyl peroxide (DCP) radical initiator system with limonene. The autooxidation worked as an amplifier to produce more alkyl radical species in the grafting reaction, and the existence of the MWNTs and the limonene suppressed the side reaction. In addition, the existence of the limonene suppressed the oxidation of the MWNT surface. The composite obtained was assessed in comparison with a PB/MWNT composite and a composite of PB/MWNT modified by Nd₂O₃/DCP without limonene using some spectroscopic methods, optical and electron microscopes, a thermal analyzer and tensile testing. The novel preparation produced a well dispersed nanocomposite compared with the other preparations. The modified MWNT surface was tightly linked to the PB matrix, so that the tensile properties of the composite showed a dependence on MWNT content. Copyright © 2011 Society of Chemical Industry     

A study of radical graft copolymerization on polypropylene during extrusion using two peroxide initiators

Functionalization of polypropylene (PP) during melt extrusion has been explored extensively. In this study, two different radical initiators were employed and compared in grafting acyclic halamine precursors to PP. 2,4‐Diamino‐6‐diallylamino‐1,3,5‐triazine (NDAM) was grafted onto PP during a melt‐extrusion process using either 2,5‐dimethyl‐2,5‐(tert‐butylperoxy)hexyne (DTBHY) or dicumyl peroxide (DCP) as initiator. The results confirmed the radical graft copolymerization of the monomer onto the PP backbone during the reactive extrusion process. It was revealed that, at low monomer concentration, when peroxide initiator concentration was increased, polymer chain scission became dominant. DCP was more efficient than DTBHY as an initiator in the graft polymerization. After exposure to chlorine bleach, the grafted structures could be easily transformed into N‐halamines, which provided powerful, durable and regenerable antibacterial activities against Escherichia coli and Staphylococcus aureus. It is concluded that both DCP and DTBHY could be used as radical initiators in reactive extrusion to graft certain vinyl monomers to PP. The NDAM‐grafted PP could provide expected antibacterial function after chlorination of the grafted product in a chlorine bleach solution. The modified PP showed great potential for use in medical devices and non‐woven textiles. Copyright © 2009 Society of Chemical Industry     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Microwave promoted synthesis of chitosan‐graft‐poly(acrylonitrile)

Using microwave (MW) irradiation, polyacrylonitrile was grafted onto chitosan with 170% grafting yield under homogeneous conditions in 1.5 min in the absence of any radical initiator or catalyst. Under similar conditions a maximum grafting of 105% could be achieved when the K₂S₂O₈/ascorbic acid redox system was used as radical initiator in a thermostatic water bath at 35 ± 2°C. The representative graft copolymer was characterized by Fourier transform infrared spectra, thermogravimetric analysis, and X‐ray diffraction measurement, taking chitosan as a reference. The effects of such reaction variables as monomer/chitosan concentration, MW power, and exposure time on the graft co polymerization were studied. A probable mechanism for grafting without the redox system under microwaves was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 820–825, 2005     

Synthesis of lactose‐containing glycopolymer‐grafted silica gel particles

The surface free‐radical graft polymerization of 2‐O‐meth‐acryloyloxyethoxyl‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐galactopyranosyl)‐(1‐4)‐2,3,6‐tri‐O‐acetyl‐β‐D ‐glucopyranoside onto silica gel particles has been carried out with azobis (isobutyronitrile) as initiator. The grafting reaction conditions and the glycopolymer‐grafted silica gel particles have been investigated in detail. Chromatographic experiments have been attempted on glycopolymer‐modified silica gel particles as a stationary phase under normal phase conditions, and it was found that a certain separation effect of the quercetin and its derivant isorhamnetin was achieved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Solvothermal process for grafting dibutylmaleate onto poly(ethylene‐co‐1‐octene)

Solvothermal process was successfully developed to graft dibutylmaleate (DBM) onto poly(ethylene‐co‐1‐octene) (POE) with dicumyl peroxide (DCP) as free radical‐initiator. FTIR spectra demonstrate that DBM is successfully grafted onto the backbone of POE by this novel method. The influences of DBM content, DCP concentration, POE concentration, reaction temperature and reaction time on the grafting copolymerization have been investigated in detail through grafting degree (GD). It is worthy to indicate that high grafting degree (above 15%) can be achieved through the one‐pot way when the graft reaction is carried out in 40 mL toluene at 150°C for 5 h with 1.6 g DBM, 6–8 g POE and 0.35 g DCP. This developed solvothermal process is becoming an effective way to prepare POE‐g‐DBM graft copolymers, and can be extended to other systems. In addition, TGA results show that the thermal properties of POE are enhanced after the grafting reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of Electrical Conductivity of Trivalent Rare‐earth Cation‐doped Neodymium Zirconate by Co‐doping Gadolinium and Ytterbium

Pyrochlore oxides of A₂Zr₂O₇, where A represents trivalent rare‐earth elements, have a high electrical conductivity, which makes them suitable for applications as high‐temperature solid electrolytes. The influence of Gd and Yb cations co‐doping at the Nd site on structure and electrical conductivity of a pyrochlore oxide Nd₂Zr₂O₇ is investigated using X‐ray diffraction and impedance spectra measurements. Different zirconate ceramics of Nd₂Zr₂O₇, Nd_1.8Gd_0.2Zr₂O₇, Nd_1.8Gd_0.1Yb_0.1Zr₂O₇, Nd_1.4Gd_0.6Zr₂O₇ and Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ are prepared by pressureless‐sintering method at 1,973 K for 10 h in air. Nd₂Zr₂O₇ doped with Gd and Yb cations at the Nd site exhibit a single phase of pyrochlore‐type structure. The measured values of the total conductivity obey the Arrhenius relation. Nd₂Zr₂O₇ and its doped zirconate ceramics are oxide‐ion conductors in the oxygen partial pressure range of 1.0 × 10^–4 to 1.0 atm at all test temperature levels. The total conductivity increases with reducing average ionic radii of A‐site rare‐earth cations. The dual Yb+Gd intermix doping causes a distinctly enhanced total conductivity as compared to unmodified Nd₂Zr₂O₇ and singly Gd‐doped zirconate ceramics. The highest total conductivity value obtained in this work is 1.02 × 10^–2 S cm × ¹ at 1,173 K for Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ ceramic.     

Morphology and mechanical properties of ABS blends prepared from emulsion‐polymerized PB‐g‐SAN impact modifier with AIBN as initiator

A series of PB‐g‐SAN impact modifiers (polybutadiene particles grafted by styrene and acrylonitrile) are synthesized by seed emulsion copolymerization initiated by oil‐soluble initiator, azobisiobutyronitrile (AIBN). The ABS blends are obtained by mixing SAN resin with PB‐g‐SAN impact modifiers. The mechanical behavior and the phase morphology of ABS blends are investigated. The graft degree (GD) and grafting efficiency (GE) are investigated, and the high GD shows that AIBN has a fine initiating ability in emulsion grafting of PB‐g‐SAN impact modifiers. The morphology of the rubber particles is observed by the transmission electron microscopy (TEM). The TEM photograph shows that the PB‐g‐SAN impact modifier initiated by AIBN is more likely to form subinclusion inside the rubber particles. The dynamic mechanical analysis on ABS blends shows that the subinclusion inside the rubber phase strongly influences the T_g, maximum tan δ, and the storage modulus of the rubber phase. The mechanical test indicates that the ABS blends, which have the small and uniform subinclusions dispersed in the rubber particles, have the maximum impact strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Enzyme‐mediated grafting of acrylamide to ultrahigh molecular weight polyethylene fiber: A novel radical initiation system

The enzyme‐mediated grafting of acrylamide (AM) to ultrahigh molecular weight polyethylene (UHMWPE) fibers using horseradish peroxidase (HRP) was demonstrated. To optimize the reaction condition, the concentrations of monomer, H₂O₂, the initiator, and time were varied. The grafting results were discussed and a reaction mechanism was proposed. Function groups and structural change of the graft copolymer were determined by FTIR spectroscopic and scanning electron microscopy micrographs for proof of grafting and the results were discussed. Results show that the surface of treated fiber becomes rougher than the untreated surface. Compared to unmodified fiber, modified fiber surface had significantly increased the interfacial shear strength, and carbonyl‐stretching regions in the IR spectra. The interfacial shear strength of the UHMWPE fiber increased, clearly indicating that enzymatic‐grafted acrylamide could significantly increase the hydrophilicity of the surfaces of UHMWPE fibers. Moreover, the hydrophilicity of treated fiber depends on the monomer concentration, the initiator concentration, and oxidizing agent concentration as well as the time of the reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1011–1016, 2005     

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

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

Synthesis of tercopolymer BA–MMA–VTES and surface modification of nano‐size Si3N4 with this macromolecular coupling agent

A new macromolecular coupling agent butyl acrylate (BA)‐methyl methacrylate (MMA)‐vinyl triethoxy silane (VTES) tercopolymer was synthesized using solution polymerization initiated by free radical initiator benzoyl peroxide (BPO) and dicumyl peroxide (DCP). Dodecylthiol is choosed as the chain transfer to control the molecule weight of this tercopolymer. The terpolymer's molecular structure was confirmed by FTIR and NMR, and its average molecular weight was determined by GPC. In this work, the tercopolymer BA–MMA–VTES is used for surface modification of silicon nitride (Si₃N₄) nanopowder. The structure surface properties and thermal stability of modified nano‐Si₃N₄ were systematically investigated by FTIR, TGA, TEM, and size distribution analyzer. The results show that the macromolecular coupling agent bonds covalently on the surface of nano‐sized Si₃N₄ particles and an organic coating layer is formed. The optimum loading of this macromolecular coupling agent BA–MMA–VTES tercopolymer is 5% (wt %) of nano‐sized Si₃N₄. TEM also reveals that modified nano‐Si₃N₄ possesses good dispersibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melt grafting of n‐butyl methacrylate onto poly(vinyl chloride): Synthesis and characterization*

The graft copolymerization of n‐butyl methacrylate monomer onto compounded poly(vinyl chloride) was carried out by melt‐mixing process in a Brabender plasticorder (BPCR) using a free‐radical initiator. The reaction conditions such as initiator and monomer concentration, shear rate (rpm), residence time, and temperature were optimized in the mixing head of BPCR attached to a torque rheometer. The graft copolymers were Soxhlet extracted with cyclohexane and were characterized by intrinsic viscosity, FTIR, and ¹³C‐NMR spectroscopy. A maximum of 14% grafting was obtained. The graft copolymer showed significant improvement in processibility and both thermal and mechanical properties. Scale‐up studies of the optimized recipe were carried out in a single‐screw extruder for commercial trials/evaluation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2442–2449, 2004     

Reactive melt blending of PS‐POSS hybrid nanocomposites

Hybrid nanocomposites of polystyrene (PS) and methacryl phenyl polyhedral oligomeric silsesquioxane (POSS) were synthesized by reactive melt blending in the mixing chamber of a torque rheometer using dicumyl peroxide (DCP) as a free radical initiator and styrene monomer as a chain transfer agent. The effects of mixing intensity and composition on the molecular structure and morphology of the PS‐POSS hybrid nanocomposites were investigated. The degree of POSS hybridization (α_POSS) was found to increase with the POSS content, DCP/POSS ratio, and rotor speed. For the PS‐POSS materials processed in the absence of styrene monomer, an increase in the α_POSS led to a reduction in the molecular weight by PS chain scission, as a consequence of the free radical initiation. On the other hand, the use of styrene monomer as a chain transfer agent reduces the steric hindrance in the hybridization reaction between POSS and PS, enhancing the degree of POSS hybridization and avoiding PS degradation. The PS‐POSS morphology consists of nanoscale POSS clusters and particles and microscale crystalline POSS aggregates. PS‐POSS with higher α_POSS values and lower amounts of nonbound POSS showed improved POSS dispersion, characterized by smaller interfacial thickness (t) and greater Porod inhomogeneity lengths (l_p). The processing‐molecular structure–morphology correlations analyzed in this study allow the POSS dispersion level in the PS‐POSS materials to be tuned by controlling the reactive melt blending through the choice of the processing conditions. These insights are very useful for the development of PS‐POSS materials with optimized performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization of morphology in chemically modified styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene by solid‐state nuclear magnetic resonance

Multiphase triblock styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) copolymers chemically modified with maleic anhydride (MAH) in the presence of a radical initiator by reactive extrusion were studied by solid‐state ¹H‐NMR and ¹³C‐NMR. In the experiments performed, the concentrations of MAH and initiator were kept constant, whereas the temperature profile in the extruder was varied. Samples with known extents of grafting and crosslinking were analyzed with NMR with techniques based on proton spin diffusion to investigate the microphase structure of the modified copolymers. The ¹³C‐NMR results show that the size of the rigid domains was about 15 nm and was not significantly changed by the modification. Alterations in the rubbery phase were illustrated by measured changes in proton spin‐spin (T₂) relaxation times. The fraction of protons having intermediate mobilities increased slightly in modified SEBS with respect to that observed in unmodified copolymers. These results were found to be independent of the extruder temperature profiles used, at least in the range studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface‐modified polysulfone membranes: Aqueous phase oxidation via persulfate radical

Polysulfone (Udel P1800) ultrafiltration membranes were surface modified using potassium persulfate (K₂S₂O₈) as a free radical source in the aqueous phase. The expected modification was hydrogen abstraction leading to hydroxylation at one or two sites on the isopropylidene linkage. Reaction time, K₂S₂O₈ concentration, and temperature were optimized based on two criteria: (1) minimal change in pure water fluxes after surface modification and (2) reduction of adsorptive fouling with a pulp mill effluent. The pure water flux retention for an unmodified membrane was ～20% after adsorptive fouling with the pulp mill effluent and was increased to 70% after reaction with K₂S₂O₈. Angle‐resolved XPS indicated increased oxygen and a new carbon peak consistent with an aldehyde reaction occurring in the top 3.5 nm. NMR solution analysis was inconclusive because of the low sensitivity of the experiment. Further analysis of oxidation products was carried out on finely dispersed polymer. Fourier transform infrared, internal reflection spectroscopy suggested oxidation by the formation of an aldehyde which was further oxidized to carboxylic acid. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1723–1730, 2006     

Advance polymeric carbon nanocomposite films with enhanced thermo‐mechanical properties

The homogenous nanocomposite films of UV/O₃ oxidized multiwall carbon nanotubes (MWCNTs) subsequently modified with aniline moiety were synthesized with polymethylmethacrylate (PMMA) through free radical polymerization. The phenylamine functional groups present on the surface of MWCNTs providing an anchoring sites for deposition of Ag metal nanoparticles (NP).The in situ free radical polymerization of MMA in the presence of these well dispersed nanotubes gave a new class of radiation resistant nanocomposite films. The synthesized materials were characterized by FT‐IR, TGA, TEM, EDX, TC, DMA, universal testing machine, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. The microscopic and structural properties reflect the homogenous mixing of modified MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% addition of modified nanofiller. Thermal and thermo‐mechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films have been compared with neat polymer. The results revealed that modified nanofiller network can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Fully renewable limonene‐derived polycarbonate as a high‐performance alkyd resin

Limonene‐derived polycarbonate‐based alkyd resins (ARs) have been prepared by copolymerization of limonene dioxide with CO₂, catalysed by a β‐diiminate zinc–bis(trimethylsilyl)amido complex, and subsequent chemical modification with soybean oil fatty acids using triphenylethylphosphonium bromide as the catalyst. This quantitative partial modification was realized via epoxy–carboxylic acid chemistry, affording ARs with higher oil lengths, lower polydispersities and higher glass transition temperatures (T_g) in comparison to a conventional polyester AR based on phthalic acid, multifunctional polyol pentaerythritol and soybean fatty acid. The novel limonene polycarbonate AR and the conventional polyester AR were evaluated as coatings and both the physical drying (without the presence of the oxidative drying accelerator Borchi® Oxy Coat) and chemical curing (with Borchi® Oxy Coat) processes of these coatings were monitored by measuring the König hardness and complex modulus development with time. A better performance was obtained for the alkyd paint containing polycarbonates modified with fatty acids (FA‐PCs), which showed a faster chemical drying, a higher König hardness and a higher T_g in coating evaluation, demonstrating that the fully renewable FA‐PCs are promising resins for alkyd paint applications. © 2019 Society of Chemical Industry     

Effects of rare earth samarium oxide on the properties of polypropylene‐graft‐cardanol grafted by reactive extrusion

Rare earth elements can improve the performance of polymers because of their special 4f orbitals. The nucleation and stabilization of radical groups of rare earth particles can affect the structure of polypropylene (PP) and its properties. In this study, samarium oxide (Sm₂O₃) particles were used as a cocatalyst and nucleating agent in polypropylene‐graft‐cardanol (CAPP) grafted by reactive extrusion. The properties of polypropylene‐graft‐cardanol containing modified Sm₂O₃ with a titanate coupling agent (CAPPMS) were investigated by ultraviolet–visible spectrometry, polarizing microscopy, differential scanning calorimetry, scanning electron microscopy, universal testing, and capillary rheometry with the reference of CAPP containing unmodified Sm₂O₃ particles. The results show that the titanate coupling agent (TCA‐401) coated on the surface of the Sm₂O₃ particles improved the dispersion of the Sm₂O₃ particles and the adhesion between the Sm₂O₃ particles and CAPP matrix. The Sm₂O₃ particles promoted more cardanol to graft onto PP. Acting as nucleator for CAPP, the Sm₂O₃ particles increased the crystallization rate, increased the melting temperature, and decreased the spherulite size of CAPP. The modified Sm₂O₃ particles showed a greater effect on the mechanical and rheological properties than the unmodified Sm₂O₃ particles did. The tensile strength, impact strength and flexural strength of CAPPMS increased by 10 MPa, 0.64 kJ/m², and 6.5 MPa, respectively, compared to those of CAPP when we used 4.5 mol % modified Sm₂O₃ particles. The viscosity of CAPPMS increased to a certain extent in the presence of the modified Sm₂O₃. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41012.