Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 15

1 August 2005

Volume 43, Issue 15

Pages 3189–3459

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      Design strategies for controlling the molecular weight and rate using reversible addition–fragmentation chain transfer mediated living radical polymerization (pages 3189–3204)

      Michael J. Monteiro

      Version of Record online: 17 JUN 2005 | DOI: 10.1002/pola.20845

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      The use of living radical polymerization has led to many new and unique polymer architectures. Reversible addition–fragmentation chain transfer (RAFT) polymerization is the most versatile but is also the most mechanistically complex. To unravel the mechanism, kinetic simulations, allowing aspects of the mechanism that are not intuitive to be understood, have been carried out. This article discusses the effect of the RAFT agent's reactivity on the rate and evolution of the molecular weight distribution.

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    1. Reactivity of oxetane monomers in photoinitiated cationic polymerization (pages 3205–3220)

      Umut Bulut and James V. Crivello

      Version of Record online: 17 JUN 2005 | DOI: 10.1002/pola.20723

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      3,3-Disubstituted oxetanes display long induction periods during their photoinitiated cationic ring-opening polymerizations with strong Brønsted acid generating photoinitiators. Investigations have shown that the induction periods are due to the formation of long-lived tertiary oxonium ions. The further reaction of these species with the monomer is the slowest step in the reaction sequence shown. Several methods for shortening the induction period have been explored.

    2. Synthesis of colloidal superparamagnetic nanocomposites by grafting poly(ϵ-caprolactone) from the surface of organosilane-modified maghemite nanoparticles (pages 3221–3231)

      C. Flesch, E. Bourgeat-Lami, S. Mornet, E. Duguet, C. Delaite and P. Dumas

      Version of Record online: 15 JUN 2005 | DOI: 10.1002/pola.20772

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      The ring-opening polymerization of ϵ-caprolactone was initiated from amino groups immobilized at the surface of maghemite nanoparticles in the presence of aluminum isopropoxide or tin octoate. The amount of grafted polymer depended on the monomer concentration and the amino-to-metal ratio. The covalently anchored polyester shell provided biocompatible properties to the superparamagnetic iron oxide.

    3. Influence of molecular weight on liquid crystalline behavior of linear and star mesogen-jacketed liquid crystal polymers (pages 3232–3244)

      Xingzhu Wang, Hailiang Zhang, Erqiang Chen, Xiayu Wang and Qifeng Zhou

      Version of Record online: 17 JUN 2005 | DOI: 10.1002/pola.20743

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      A series of novel multi-armed (di-, tri- and tetra-armed) mesogen-jacketed liquid crystal polymers (MJLCPs) were synthesized by atom transfer radical polymerization (ATRP) of {2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}(MPCS) using di-, tri- and tetrafunctional initiator, respectively. The chemical structures of these multi-armed mesogen-jacketed liquid crystal polymers were confirmed by 1H NMR. The liquid crystalline behavior of these multi-armed MJLCPs with arms ranging from two to four was studied by DSC, POM, and wide-angle X-ray diffraction (WAXD). It was found that liquid crystalline phases appeared simply when the number molecular weights (Mn,GPC) of these multi-armed MJLCPs was higher than a certain critical values, that is, Mn,GPC > 1.87 × 104 g/mol, 1.84 × 104 g/mol, 2.69 × 104 and 3.68 × 104 g/mol, which were initiated by coil difunctional initiator, hard difunctional initiator, trifunctional initiator, and tetrafunctional initiator, respectively. All the liquid crystalline phase was found to be stable up to the decomposition temperature of these multi-armed MJLCPs.

    4. Novel thermally stable poly(amine hydrazide)s and poly(amine-1,3,4-oxadiazole)s for luminescent and electrochromic materials (pages 3245–3256)

      Guey-Sheng Liou, Sheng-Huei Hsiao and Tzy-Hsiang Su

      Version of Record online: 17 JUN 2005 | DOI: 10.1002/pola.20808

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      Four new triphenylamine-based poly(amine hydrazide)s were prepared from the combination of two dicarboxylic acids, 4,4′-dicarboxy-4″-N,N-diphenylaminotriphenylamine and 4,4′-dicarboxytriphenylamine, with two diacyl hydrazide monomers, terephthalic dihydrazide and isophthalic dihydrazide. These poly(amine hydrazide)s were amorphous and soluble in common organic solvents and could be solution-cast into transparent and flexible films with good mechanical properties. Subsequent thermal cyclodehydration of the poly(amine hydrazide)s afforded the corresponding poly(amine-1,3,4-oxadiazole)s. These poly(amine hydrazide)s exhibited high intensity of photoluminescence both in solutions and as cast films. The hole-transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Thin films of all obtained poly(amine hydrazide)s and poly(amine-1,3,4-oxadiazole)s revealed reversible electrochromic behavior when a linear potential sweep was applied, changing color from original pale yellow to green and then to blue at electrode potentials of 0.87 and 1.26 V, respectively.

    5. Synthesis, characterization, and utilization of itaconate-based polymerizable surfactants for the preparation of surface-carboxylated polystyrene latexes (pages 3257–3267)

      R. Arun Prasath and S. Ramakrishnan

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20768

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      Surface carboxylated uncrosslinked and crosslinked polystyrene latexes were prepared using two polymerizable surfactants (surfmers), namely, monododecyl itaconate (MDDI) and monocetyl itaconate (MCI). The size of latex varied between 41–72 nm and was seen to depend inversely on the surfmer concentration. Conclusive evidence for their incorporation, in the case of the soluble polystyrene latexes, came from solution 1H NMR studies and conductometric titrations of surface carboxylic acid functionality. Smaller-size latexes with higher surface functional group density exhibited enhanced stability to increased ionic strength and freeze-thaw cycles.

    6. Copolymerization of ε-caprolactone and glycolide—A comparison of bismuth(III) hexanoate and tin(II) octanoate as initiators (pages 3268–3277)

      Hans R. Kricheldorf and Heiko Hachmann-Thiessen

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20795

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      Copolymerization of ε-caprolactone and glycolide was performed in bulk initiated by either tin(II) 2-ethylhexanoate or bismuth(III) n-hexanoate. The copolyesters prepared via bismuth salts contained a significantly higher content of alternating sequences and, because of their reduced blockiness, a higher solubility in organic solvents.

    7. Hyperbranched polyesters based on polycondensation of 1,3,5-tris(2-hydroxyethyl) cyanuric acid and 3,5-dihydroxybenzoic acid (pages 3278–3288)

      S. H. Mansour, N. N. Rozik, K. Dirnberger and N. E. Ikladious

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20788

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      A series of hyperbranched polyesters were produced by the condensation of 3,5-dihydroxybenzoic acid with 1,3,5-tris(2-hydroxyethyl) cyanuric acid as a trifunctional central core. The monomer-to-core ratio was varied between 3 and 45. The degree of branching of the polyesters was found to be in the range of 0.7–0.8. The number-average molecular weights calculated via 1H NMR spectroscopic degree-of-polymerization values are in reasonable agreement with the predicted values derived from the monomer-to-core ratio for all prepared polyesters. Thermal and photophysical properties were also studied. The polyesters were blue emitter, and the solution exhibited intense fluorescence, with a maximum of 430 nm.

    8. New π-stacked benzofulvene polymer showing thermoreversible polymerization: Studies in macromolecular and aggregate structures and polymerization mechanism (pages 3289–3304)

      Andrea Cappelli, Maurizio Anzini, Salvatore Vomero, Alessandro Donati, Lucia Zetta, Raniero Mendichi, Mario Casolaro, Pietro Lupetti, Paolo Salvatici and Gianluca Giorgi

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20783

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      The macromolecular and aggregate structures of poly[ethyl 1-methylene-3-(4-methylphenyl)-1H-indene-2-carboxylate] (poly-BF1), a new polymer based on a functionalized benzofulvene moiety, have been investigated with NMR spectroscopy, absorption and emission spectrophotometry, and transmission electron microscopy (TEM). The collected evidence is consistent in indicating for poly-BF1 a vinyl (1,2) polymer structure stabilized by means of aromatic stacking interactions. Furthermore, TEM studies performed on metal replicas have shown that the polymer is liable to give nanostructured aggregates.

    9. Influence of the cocatalyst structure on the statistical copolymerization of methyl methacrylate with bulky methacrylates using the zirconocene complex Cp2ZrMe2 (pages 3305–3314)

      Konstantinos Kostakis, Stylianos Mourmouris, Konstantinos Kotakis, Nikolaos Nikogeorgos, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/pola.20820

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      Two different borate cocatalysts were employed to study their effects on the statistical copolymerization of methyl methacrylate with cyclohexyl methacrylate and trimethylsilyloxyethyl methacrylate with the zirconocene precursor Cp2ZrMe2. The reactivity ratios of methyl methacrylate and these methacrylates were calculated with the Finemann–Ross, inverted Finemann–Ross, and Kelen–Tüdos graphical methods. The structural parameters of the copolymers were estimated from the calculation of the dyad monomer sequence fractions.

    10. Preparation and phase behavior of side-chain cholesteric liquid-crystalline elastomers (pages 3315–3323)

      Jian-She Hu, Bao-Yan Zhang, Ai-Juan Zhou, Yan-Li Dong and Zhan-Xiang Zhao

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/pola.20784

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      New monomers M1, M2, and a series of cholesteric elastomers were synthesized and characterized. The mesomorphic properties and phase behavior were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction. M1 showed a cholesteric phase, and M2 displayed smectic and nematic phases. Elastomers containing <15 mol % of the crosslinking units showed reversible cholesteric phase transition, wide mesophase temperature ranges, and high thermal stability phase. Tg increased, and Ti and ΔT of the elastomers decreased with increasing content of the crosslinking unit.

    11. Photocycloaddition-induced preparation of nanostructured, cyclic polymers using biscinnamated or biscoumarinated oligo(ethylene glycol)s (pages 3324–3336)

      Y. Nakayama and T. Matsuda

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/pola.20774

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      Two types of photoreactive water-soluble oligo(ethylene glycol)s (OEGs; Mn = ca. 6500) were prepared by derivatization of OEG with photodimerizable groups such as cinnamates or coumarinates at both ends. The molecular design of nanostructured, cyclic polymers of various sizes is possible by changing the concentration of aqueous solutions and cast solvents in this photoaddition system of biscoumarinated OEGs.

    12. Polymerization of acrylates and bulky methacrylates with the use of zirconocene precursors: Block copolymers with methyl methacrylate (pages 3337–3348)

      Konstantinos Kostakis, Stylianos Mourmouris, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 23 JUN 2005 | DOI: 10.1002/pola.20825

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      The polymerization of cyclohexyl methacrylate, trimethylsilyloxyethyl methacrylate, n-butyl acrylate, and tert-butyl acrylate was studied with different catalytic systems based on zirconocene complexes. Rather well-defined block copolymers of these monomers with methyl methacrylate were synthesized.

    13. Effect of ligand on the synthesis of star polymers by resorcinarene-based ATRP initiators (pages 3349–3358)

      Satu Strandman, Petri Pulkkinen and Heikki Tenhu

      Version of Record online: 24 JUN 2005 | DOI: 10.1002/pola.20804

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      The effect of steric hindrance on the initiating properties of two multifunctional resorcinarene-based initiators in atom transfer radical polymerization (ATRP) was studied by using Cu(I)-complexes of three multidentate amine ligands in the polymerization of tert-butyl acrylate and methyl methacrylate. These ligands are less sterically hindered and have higher activities in the catalysis of ATRP of (meth)acrylates than 2,2′-bipyridine. The polymerizations were faster and more controlled than with the 2,2′-bipyridyl catalyst, but the tendency for bimolecular coupling increased. Even though the initiator was octafunctional, the resulting star polymers had only four arms. This indicates that the steric hindrance arising from the conformations of the initiators determines the structure of the polymer, but the ligand noticeably affects the controllability of the polymerization.

    14. Proton transportation in an organic–inorganic hybrid polymer electrolyte based on a polysiloxane/poly(allylamine) network (pages 3359–3367)

      Ping-Lin Kuo, Wei-Fu Chen and Wuu-Jyh Liang

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20754

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      A new class of proton-conducting polymer was developed via the sol–gel process by the treatment of poly(allylamine) with 3-glycidoxypropyltrimethoxysilane doped with ortho-phosphoric acid. The polymer matrix contains many hydrophilic sites and consists of a double-crosslinked framework of polysiloxane and amine/epoxide. The polymer morphology was investigated with IR, differential scanning calorimetry, and solid-state NMR. The hybrid polymers have high proton conductivity, especially in a high-temperature range.

    15. Unique catalytic behavior of chromium complexes having halogenated bis(imino)pyridine ligands for ethylene polymerization (pages 3368–3375)

      Yuushou Nakayama, Kenji Sogo, Hajime Yasuda and Takeshi Shiono

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20767

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      A series of {bis(imino)pyridine}chromium(III) trichloride complexes, {2,6-(RN[DOUBLE BOND]CMe)2C5H3N}CrCl3, was synthesized, and was shown to be a highly active catalyst for ethylene polymerization in the presence of MMAO. A pentafluorophenyl complex system produced moderately branched polyethylene with only ethyl branches, while the complexes with bulky substituents gave linear polyethylene.

    16. Structural and end-group effects on bulk and surface properties of hyperbranched poly(urea urethane)s (pages 3376–3393)

      Mona Abd Elrehim, Brigitte Voit, Bernd Bruchmann, Klaus-Jochen Eichhorn, Karina Grundke and C. Bellmann

      Version of Record online: 21 JUN 2005 | DOI: 10.1002/pola.20822

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      The bulk properties of aromatic and aliphatic hyperbranched poly(urea urethane)s with different end groups, in comparison with their linear analogues, were studied with differential scanning calorimetry, thermogravimetric analysis, and temperature-dependent Fourier transform infrared measurements. Polymer films were examined with microglider, contact-angle, and zeta-potential measurements. For all samples, the properties were mainly governed by the strong interactions of the urea and urethane units within the backbone, whereas the influence of the nature of the end groups and of the branched structure was reduced in comparison with other hyperbranched polymer systems.

    17. Structures and properties of liquid-crystalline polymers based on laterally attached oligo p-phenylenes (pages 3394–3402)

      Xuehong Lu, Chaobin He, Puwei Liu and Anslem C. Griffin

      Version of Record online: 24 JUN 2005 | DOI: 10.1002/pola.20841

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      Polymers consisting of laterally attached p-terphenyl and p-pentaphenyl exhibit liquid crystallinity. The polymers have good solubility and emit blue light in the solid state. An interdigitated packing structure of mesogenic groups has been proposed to represent the structure of the polymer in the oriented state.

    18. Palladium-catalyzed three-component coupling polycondensation of aromatic diiodide, aromatic bis(boronic acid propanediol ester), and norbornadiene: A new route for poly(p-phenylene vinylene) (pages 3403–3410)

      Satoko Ishibe and Ikuyoshi Tomita

      Version of Record online: 22 JUN 2005 | DOI: 10.1002/pola.20849

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      A novel synthetic method for soluble precursor polymers of poly(p-phenylene vinylene) (PPV) derivatives by the palladium-catalyzed three-component coupling polycondensation of aromatic diiodides, aromatic bis(boronic acid) derivatives, and norbornadiene is described. The displayed retro Diels–Alder reaction produced PPV at 200 °C in vacuo.

    19. First diphosphinoamine ligand bearing a polymerizable side chain: Complexation with copper(I) (pages 3411–3420)

      Ritu Ahuja and Ashoka G. Samuelson

      Version of Record online: 24 JUN 2005 | DOI: 10.1002/pola.20724

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      A diphosphinoamine ligand with a polymerizable side chain, (PPh2)2N[BOND]CH2[BOND]C6H4[BOND]CH[DOUBLE BOND]CH2 (1), was synthesized for the first time. The ligand could be polymerized by anionic polymerization with n-butyllithium with number-average and weight-average molecular weights of 40,050 and 55,690, respectively, and a polydispersity index of 1.39. The phosphine ligand was readily complexed to metals, as shown by the formation of a copper(I) complex upon the addition of [Cu(CH3CN)4]ClO4, and this resulted in a crosslinked polymer.

    20. Cationic copolymerization of cycloaliphatic epoxy resin with a spirobislactone with lanthanum triflate as initiator: I. Characterization and shrinkage (pages 3421–3432)

      Xavier Fernandez, Josep Maria Salla, Angels Serra, Ana Mantecón and Xavier Ramis

      Version of Record online: 24 JUN 2005 | DOI: 10.1002/pola.20801

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      3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECH) was cured with different proportions of 1,6-dioxaspiro[4,4]nonane-2,7-dione (s(γ-BL)) using lanthanum triflate as a catalyst. The shrinkage undergone during curing was monitored by means of thermomechanical analysis in isothermal experiments. FTIR/ATR spectroscopy was used to study the evolution of lactone, epoxide, and intermediate spiroorthoester (SOE) groups in order to identify the different reactions that take place during the curing process. DSC was used to study the thermal characteristics of the curing process and to assess the glass-transition temperature of the cured material. The dynamic mechanical properties of the cured material were determined based on the data obtained by DMTA.

    21. Synthesis and characterization of micron-sized monodisperse superparamagnetic polymer particles with amino groups (pages 3433–3439)

      Zhiya Ma, Yueping Guan and Huizhou Liu

      Version of Record online: 24 JUN 2005 | DOI: 10.1002/pola.20803

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      A novel and easy method has been developed for preparation of monodisperse magnetic PGMA particles with amino groups. The process involved the preparation of parent PGMA particles, chemical modification with EDA, and subsequent precipitation of iron ions impregnating within the particles to form magnetite. The magnetic particles were fully characterized with regard to their morphology, magnetic properties, and composition by SEM, TEM, VSM, FTIR, and XRD. The particles had the number-average size of 2.6 μm and quite narrow size distribution. They had superparamagnetism and saturation magnetization of 16.3 emu/g.

    22. Properties of well-defined alternating and random copolymers of methacrylates and styrene prepared by controlled/living radical polymerization (pages 3440–3446)

      Betül Kirci Denizli, Jean-François Lutz, Lidia Okrasa, Tadeusz Pakula, Ali Guner and Krzysztof Matyjaszewski

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20824

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      The properties of well-defined alternating copolymers poly(methyl methacrylate-alt-styrene) and poly(n-butyl methacrylate-alt-styrene), prepared by reversible addition–fragmentation chain transfer in the presence of Lewis acids, were investigated. The physical properties were compared with those of random copolymers of the same overall composition and the corresponding homopolymers. Wide-angle X-ray scattering data showed that the alternating copolymers possessed a more regular comonomer sequence than the random copolymers. The thermomechanical properties of alternating copolymers and random copolymers were quite similar and typical for the amorphous polymers, but glass-transition temperature for alternating copolymer was remarkably different from that for the random copolymer.

    23. Fluorescein–formaldehyde oligomeric pH indicator: Facile synthesis, characterization, and potential application (pages 3447–3453)

      Zhihong Liu, Shuyu Gao and Tianlu Chen

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20850

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      A kind of fluorescent oligomeric pH indicator (fluorescein–formaldehyde product) was synthesized by the reaction of fluorescein with formaldehyde under alkaline conditions by a one-pot method. The synthesized product was fully characterized with Fourier transform infrared, 1H NMR, ultraviolet–visible spectra, luminescence spectra, and matrix-assisted laser desorption/ionization time-of-flight mass spectra. The results indicated that the fluorescein–formaldehyde product contained dimer, trimer, tetramer, and even a litter octamer. Visible spectra and luminescence spectra showed that the fluorescein–formaldehyde product could still provide pH sensitivity similar to that of fluorescein. In addition, the oligomeric pH indicator immobilized poly(vinyl alcohol) membranes could be easily fabricated. Thus, they are promising transparent membranes for optical pH sensors of a wide pH range (0.0–10.0) based on absorption and fluorescence.

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    1. Radical polymerization in a chiral ionic liquid: Atom transfer radical polymerization of acrylates (pages 3454–3459)

      Tadeusz Biedroń and Przemysław Kubisa

      Version of Record online: 20 JUN 2005 | DOI: 10.1002/pola.20863

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      A simple synthetic method was applied to the synthesis of a chiral ionic liquid containing a center of chirality in a cationic fragment from easily available starting compounds. This chiral ionic liquid was used as a solvent for the atom transfer radical polymerization (ATRP) of methyl and ethyl acrylate. Only a very limited effect of the chiral reaction medium on the stereochemistry of radical propagation was observed.

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