Studies on the phase structure of ethylene‐vinyl acetate copolymers by solid‐state 1H and 13C NMR

The phase structure of a series of ethylene‐vinyl acetate copolymers has been investigated by solid‐state wide‐line ¹H NMR and solid‐state high‐resolution ¹³C NMR spectroscopy. Not only the degree of crystallinity but the relative contents of the monoclinic and orthorhombic crystals within the crystalline region varied with the vinyl acetate (VA) content. Biexponential ¹³C NMR spin–lattice relaxation behavior was observed for the crystalline region of all samples. The component with longer ¹³C NMR spin–lattice relaxation time (T₁) was attributed to the internal part of the crystalline region, whereas the component with shorter ¹³C NMR T₁ to the mobile crystalline component was located between the noncrystalline region and the internal part of the crystalline region. The content of the mobile crystalline component relative to the internal part of the crystalline region increased with the VA content, showing that the ¹³C NMR spin–lattice relaxation behavior is closely related to the crystalline structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2199–2207, 2002     

Synthesis and chiral micellization behavior of optically active amphiphilic diblock copolymer bearing quinine pendants

A novel optically active amphiphilic diblock copolymer bearing quinine pendants poly(ethylene oxide)‐b‐poly(glycidyl triazolyl‐L ‐quinine) (MPEO‐b‐PGTQ) was synthesized by “click” reaction of alkyne‐modified diblock copolymer poly(ethylene oxide)‐b‐poly(glycidyl propargyl ether) (MPEO‐b‐PGPE) and 9‐N₃‐quinine. The structure and composition of copolymers were characterized by gel permeation chromatography, ¹H nuclear magnetic resonance spectroscopy (¹H NMR), elemental analysis and optical rotation measurements, which showed that the synthetic route could provide the copolymer with well‐defined composition and with similar optical activity compared to its parent quinine. The micellization behavior of this chiral copolymer was investigated in different solvent systems. The results from fluorescence spectroscopy, UV spectroscopy, dynamic light scattering, transmission electron microscopy, ¹H NMR and circular dichroism (CD) spectroscopy indicated that the MPEO‐b‐PGTQ could form regular chiral spherical micelles in H₂O and Tetrahydrofuran‐H₂O (10:90, V/V) systems, and the state of aggregated chiral micelles depended on the nature of the medium. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3640–3650, 2009     

Dual crosslinked phenylethynyl end‐capped sulfonated polyimides via the ethynyl and sulfonate groups promoted by PEG

Typically, phenylethynyl (PE) end‐capped oligomides require a temperature of 370 °C for 1 h to develop a crosslinked system. A published method using poly(ethylene glycol)s (DM‐PEG‐250 and PEG‐400) as cosolvents with NMP was effective in crosslinking the ethynyl end‐caps at 250 °C/3 h in nonsulfonated oligomides. The application of this novel crosslinked method to PE end‐capped sulfonated oligomides was effective but caused a secondary crosslinked network via the sulfonic acid groups and ethylene glycol solvents. The solid‐state ¹³C NMR spectral data on ¹³C‐labeled end‐caps in the PE‐3F‐SPI‐3 oligomide provide evidence for the ethynyl to ethynyl and ethylene oxide sulfonate ester dual crosslinked structure. Infrared spectroscopy of model compounds also provides evidence for the presence of crosslinked sulfonate ester and appended sulfonate ester side chains. ¹³C NMR also provided quantitative data on the extent of the ethynyl to ethynyl crosslinking reaction and sulfonate ester crosslinks and side chains. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Multifunctional mesoporous silica nanoparticles in poly(ethylene‐co‐vinyl acetate) for transparent heat retention films

Transparent inorganic‐polymer nanocomposite films are of tremendous current interest inemerging solar coverings including photovoltaic encapsulants and commercial greenhouse plastics, but suffer from significant radiative heat loss. This work provides a new and simple approach for controlling this heat loss by using mesoporous silica/quantum dot nanoparticles in poly(ethylene‐co‐vinyl acetate) (EVA) films. Mesoporous silica shells were grown on CdS‐ZnS quantum dot (QDs) cores using a reverse microemulsion technique, controlling the shell thickness. These mesoporous silica nanoparticles (MSNs) were then melt‐mixed with EVA pellets using a mini twin‐screw extruder and pressed into thin films of concentration variable controlled thickness. The results demonstrate that the experimental MSNs showed improved infrared and thermal wavebands retention in the EVA transparent films compared to commercial silica additives, even at lower concentrations. It was also found MSNs enhanced the quantum yield and photostability of the QDs, providing high visible light transmission and blocking of UV transmission of interest for next generation solar coatings. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 851–859     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

Block copolymers of poly(ethylene oxide) and poly(vinyl alcohol) synthesized by the RAFT methodology

A methodology for the synthesis of well‐defined poly(ethylene oxide)‐block‐poly(vinyl alcohol) (PEO‐b‐PVA) and PVA‐b‐PEO‐b‐PVA polymers was reported. Novel xanthate end‐functionalized PEOs were synthesized by a series of end‐group transformations. They were then used to mediate the reversible addition–fragmentation chain transfer polymerization of vinyl acetate to obtain well‐defined poly(ethylene oxide)‐b‐poly(vinyl acetate) (PEO‐b‐PVAc) and PVAc‐b‐PEO‐b‐PVAc. When these block copolymers were directly hydrolyzed in methanol solution of sodium hydroxide, polymers with brown color were obtained, which was due to the formation of conjugated unsaturated aldehyde structures. To circumvent these side reactions, the xanthate groups were removed by adding a primary amine before hydrolysis and the products thus obtained were white powders. The polymers were characterized by gel permeation chromatography, ¹H NMR spectroscopy and FT‐IR. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1901–1910, 2009     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Grafting of polycaprolactone onto poly(ethylene‐co‐vinyl alcohol) and application to polyethylene‐based bioerodable blends

Poly(ethylene‐co‐vinyl acetate) (EVA) powders containing 10 and 20 wt % of vinyl acetate (VAc) units was saponified in ethanol/KOH solution in a heterogeneous manner. Intermolecular interaction between vinyl alcohol(VOH) units in the produced poly(ethylene‐co‐vinyl alcohol) (EVOH) promoted the crystallization of intervening segments composed of ethylene units. Ring opening polymerization of caprolactone (CL) in the presence of EVOH gave EVOH‐g‐PCL graft copolymers with relatively short chain branches. Even though the graft copolymerization was carried out in a homogeneous solution, all the VOH units were not equally reactive for the PCL grafting. And the unreacted VOH units decreased very slowly with the graft copolymerization time. EVOH‐g‐PCL decreased the domain size of the dispersed phase in low density polyethylene (PE)/biodegradable master batch (MB) blends, and thus increased their tensile properties significantly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2561–2569, 2002     

Confined crystallization behaviors in polyethylene/silica nanocomposites: Synergetic effects of interfacial interactions and filler network

The confinement effects introduced by nanoparticles have been reported to influence the phase behaviors thus the properties of polymer nanocomposites. In this study, molecular dynamics and crystallization behaviors of polyethylene (PE) composited with three types of silica (SiO₂) nanoparticles, namely unmodified SiO₂, hydrophobically modified SiO₂, SiO₂‐APTES (3‐aminopropyltriethoxysilane) and SiO₂‐PTES (n‐propyltriethoxysilane), were systematically investigated via a combination of DSC, XRD and ¹H solid‐state NMR measurements. The suppressions in crystallization and chain mobilities of PE rank in the order of unmodified SiO₂ < SiO₂‐APTES < SiO₂‐PTES due to the increasing interfacial interactions between PE and SiO₂ nanoparticles. Additionally, independent of polymer–nanoparticle interactions, a silica network forms for all three kinds of nanocomposites when SiO₂ content reaches 83 wt %. The mobilities of polymer chains are severely restricted by such a percolated network structure, leading to a turning point in the crystallization ability of nanocomposites and a new crystallization peak at 45 °C lower than that of pure PE. The synergetic effects of interfacial interactions and filler network on polymer crystallization have been thoroughly studied in this work, which will provide guidance on modifying and designing nanocomposites with controlled properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 498–505     

Perfluorocarbon‐loaded shell crosslinked knedel‐like nanoparticles: Lessons regarding polymer mobility and self‐assembly

Reversible addition‐fragmentation chain transfer polymerization was employed to synthesize a set of copolymers of styrene (PS) and 2,3,4,5,6‐pentafluorostyrene (PPFS), as well as block copolymers with tert‐butyl acrylate (PtBA)‐b‐PS‐co‐PPFS, with control over molecular weight and polydispersity. It was found that the copolymerization of styrene and PFS allowed for the preparation of gradient copolymers with opposite levels of monomer consumption, depending on the feed ratio. Conversion to amphiphilic block copolymers, PAA‐b‐(PS‐co‐PPFS), by removing the protecting groups was followed by fitting with monomethoxy poly(ethylene glycol) chains. Solution‐state assembly and intramicellar crosslinking afforded shell crosslinked knedel‐like (SCK) block copolymer nanoparticles. These fluorinated nanoparticles (ca. 20 nm diameters) were studied as potential magnetic resonance imaging (MRI) contrast agents based on the ¹⁹F‐nuclei; however, it was found that packaging of the hydrophobic fluorinated polymers into the core domain restricted the mobility of the chains and prohibited ¹⁹F NMR spectroscopy when the particles were dispersed in water without an organic cosolvent. Packing of perflouro‐15‐crown‐5‐ether (PFCE) into the polymer micelle was demonstrated with good uptake efficiency; however, it was necessary to swell the core with a good solvent (DMSO) to increase the mobility and observe the ¹⁹F NMR signal of the PFCE. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1023–1037, 2009     

Ring‐opening metathesis polymerization as a route to controlled copolymers of ethylene and polar monomers: Synthesis of ethylene–vinyl chloride‐like copolymers

A series of ethylene–vinyl chloride‐like copolymers were prepared by ring‐opening metathesis polymerization (ROMP). The route to these materials included the bulk polymerization of 5‐chlorocyclooctene and 5,6‐dichlorocyclooctene with the first‐generation Grubbs' catalyst, followed by diimide hydrogenation of the resulting unsaturated polymers. In addition, the amount of chlorine in these materials was varied by the copolymerization of 5‐chlorocyclooctene with cyclooctene. These materials were fully characterized by NMR (¹H and ¹³C), gel permeation chromatography, and Fourier transform infrared spectroscopy. Finally, hydroboration was carried out on the ROMP product of 5‐chlorocyclooctene to yield a polymer, which was effectively a vinyl alcohol–vinyl chloride–ethylene terpolymer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2107–2116, 2003     

Preparation of monodisperse nanoparticles containing poly(propylene imine)(NH2)32‐polystyrene

Polypropylenimine dendrimer (DAB‐Am‐32, generation 4.0) was converted into a macroinitiator DAB‐Am‐32‐Cl via reaction with 2‐chloropropionyl chloride. Monodisperse nanoparticles containing poly(propylene imine)(NH₂)₃₂‐polystyrene were prepared by emulsion atom transfer radical polymerization (ATRP) of styrene (St), using the DAB‐Am‐32‐Cl/CuCl/bpy as initiating system. The structure of macroinitiator was characterized by FTIR spectrum, ¹H NMR, and ¹³C NMR. The structure of poly(propylene imine)(NH₂)₃₂‐polystyrene was characterized by FT‐IR spectrum and ¹H NMR; the molecular weight and molecular weight distribution of poly(propylene imine)(NH₂)₃₂‐polystyrene were characterized by gel permeation chromatograph (GPC). The morphology, size and size distribution of the nanoparticles were characterized by photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effects of monomer/macroinitiator ratio and surfactant concentration on the size and size distribution of the nanoparticles were investigated. It was found that the diameters of the nanoparticles were smaller than 100 nm (30–80 nm) and monodisperse; moreover, the particle size could be controlled by monomer/macroinitiator ratios and surfactant concentration. With the increasing of the ratio of St/DAB‐Am‐32‐Cl, the number‐average diameter (D_n), weight‐average diameter (D_w) were both increased gradually. With enhancing the surfactant concentration, the measured D_h of the nanoparticles decreased, while the polydispersity increased. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2892–2904, 2009     

Structural and dynamic study of chemically modified polyHIPE by solid‐state 13C NMR spectroscopy

The structure of laboratory‐made polyHIPEs was successfully characterized by cross‐polarity/magic‐angle spinning, solid‐state ¹³C NMR experiments. The signals of vinyl groups appeared in the spectrum of the polyHIPE precursor PH? CH?CH₂, which was prepared by the polymerization of the divinylbenzene continuous phase from a highly concentrated reverse emulsion. This material was chemically modified by the regioselective free‐radical addition of thiols to the pendant vinyl groups. Spectra of materials modified by the grafting of C₈ and C₁₂ alkyl chains, PH? SC₈ and PH? SC₁₂, respectively, were produced. The signals of the vinyl groups disappeared in favor of methylene groups. This experiment clearly established that the alkyl chains were covalently bound to the polymer. To elucidate the dynamic aspect of long chains in polyHIPE, we measured the ¹³C spin–lattice relaxation times (T₁) of PH? SC₁₂ from 25 to 100 °C with variable‐temperature, solid‐state, high‐resolution ¹³C NMR spectroscopy, revealing a strong variation in T₁ along the alkyl side chain. Furthermore, the crystallinity of a wide range of chemically modified polyHIPEs, including PH? SC₁₂, was studied with pulse ¹H NMR. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 956–963, 2001     

Graft copolymers of polyethylene by atom transfer radical polymerization

Poly(ethylene‐g‐styrene) and poly(ethylene‐g‐methyl methacrylate) graft copolymers were prepared by atom transfer radical polymerization (ATRP). Commercially available poly(ethylene‐co‐glycidyl methacrylate) was converted into ATRP macroinitiators by reaction with chloroacetic acid and 2‐bromoisobutyric acid, respectively, and the pendant‐functionalized polyolefins were used to initiate the ATRP of styrene and methyl methacrylate. In both cases, incorporation of the vinyl monomer into the graft copolymer increased with extent of the reaction. The controlled growth of the side chains was proved in the case of poly(ethylene‐g‐styrene) by the linear increase of molecular weight with conversion and low polydispersity (M_w /M_n < 1.4) of the cleaved polystyrene grafts. Both macroinitiators and graft copolymers were characterized by ¹H NMR and differential scanning calorimetry. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2440–2448, 2000     

Ethylene copolymerization with cyclic dienes using rac‐Et[Ind]2ZrCl2–Methylaluminoxane

The effect of the copolymerization temperature and amount of comonomer in the copolymerization of ethylene with 1,3‐cyclopentadiene, dicyclopentadiene, and 4‐vinyl‐1‐cyclohexene and the rac‐Et[Ind]₂ZrCl₂–methylaluminoxane metallocene system was studied. The amount of comonomer present in the reaction media influenced the catalytic activity. Dicyclopentadiene was the most reactive comonomer among the cyclic dienes studied. In general, copolymers synthesized at 60 °C showed higher catalytic activities. Ethylene–dicyclopentadiene copolymers with high comonomer contents (>9%) did not show melting temperatures. 1,3‐Cyclopentadiene dimerized into dicyclopentadiene during the copolymerization, giving a terpolymer of ethylene, cyclopentadiene, and dicyclopentadiene. A complete characterization of the products was carried out with ¹H NMR, ¹³C NMR, heteronuclear chemical shift correlation, differential scanning calorimetry, and gel permeation chromatography. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 471–485, 2002; DOI 10.1002/pola.10133     

Correlation study among oxygen permeability,molecular mobility,and amorphous structure change of poly(ethylene‐vinylalcohol copolymers) by moisture

Oxygen permeability and the free‐volume hole size (cavity size) of ethylene‐vinylalcohol copolymers (EVOH) indicate abnormal humidity dependence, that is, they have minimum values in the range of around 20–40% RH, not showing a monotonic increase with humidity. To clarify this abnormal phenomenon, we investigated its molecular mobility and amorphous structure change by means of solid‐state NMR and temperature‐modulated differential scanning calorimetry (TMDSC). The glass transition temperature (T_g) decreased with humidity. Specimens stored at 15–60% RH showed large enthalpy relaxation, and it was found that the amorphous structure became more compact and the molecular conformation became more stable by ageing within this range of humidity. Under these conditions, solid‐state NMR measurement showed a component with intermediate relaxation time in the amorphous region. The results obtained by TMDSC and solid‐state NMR showed a reduction in molecular mobility by densifying in the amorphous region under the condition of 15–60% RH. The fact that the oxygen permeability and the cavity size of EVOH indicate minimum values at low humidity are attributed to the reduction in molecular mobility by enthalpy relaxation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1181–1191, 2009     

Optical properties of the photorefractive polymeric composite with modified PVK polymer

Poly[N‐(2‐ethylhexyl)‐3‐vinylcarbazole has been synthesized by radical polymerization from N‐(2‐ethylhexyl)3‐vinyl‐carbazole. The 50‐μm thick photorefractive device containing 30 wt % piperidin‐4‐ylbenzylidene‐malononitrile showed a diffraction efficiency of 40% of 50 V/μm, which corresponded to a Δn of 0.8 × 10^?3. The photorefractive response time was τ₁ = 0.6 s. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1695–1702, 2009     

Synthesis of amphiphilic graft copolymer brush and its use as template film for the preparation of silver nanoparticles

A microphase‐separated, amphiphilic graft copolymer consisting of a poly (vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains, (PVC‐g‐POEM at 62:38 wt %) was synthesized via atom transfer radical polymerization (ATRP). Nuclear magnetic resonance (¹H NMR), FTIR spectroscopy, and transmission electron microscopy (TEM) clearly revealed that the “grafting from” method using ATRP was successful and that the graft copolymer molecularly self‐assembled into discrete nanophase domains of continuous PVC and isolated POEM regions. The self‐assembled graft copolymer film was used to template the growth of silver nanoparticles in solid state by introducing a AgCF₃SO₃ precursor and a UV irradiation process. The in situ formation of silver nanoparticles in the graft copolymer template film was confirmed by TEM, UV–visible spectroscopy, and wide angle X‐ray scattering. FTIR spectroscopy and X‐ray photoelectron spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic POEM domains, presumably due to strong interactions between the silver and the ether oxygen in POEM. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3911–3918, 2008     

Copolymerization of ethylene with linear α‐olefins by 2‐phosphinophenolate nickel catalysts

2‐Dicyclohexyl‐ and 2‐diphenylphosphinophenol, CCHH and PPHH , react with Ni(1,5‐COD)₂ to form catalysts for polymerization of ethylene in or copolymerization with α‐olefins. The more P‐basic CCHH/Ni catalyst allows concentration‐dependent incorporation of olefins to give copolymers with isolated side groups and higher molecular weights, whereas the PPHH/Ni catalyst undergoes mainly stabilizing interactions with the olefins and leads to ethylene oligomers with no or marginal olefin incorporation. Pressure–time plots of the batch reactions show that the ethylene conversion is usually slower by catalysis with CCHH/Ni than by PPHH/Ni . The microstructure of the copolymers was determined by ¹³C NMR spectra, the number of side groups per main chain was estimated by ¹H NMR analyses. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 258–266, 2009