Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 46 Issue 17

1 September 2008

Volume 46, Issue 17

Pages xxi–xxii, 5715–5975

  1. Editorial Announcement

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    1. You have free access to this content
      Editorial announcement: The 2007 SPSJ International Award of the Society of Polymer Science, Japan for Virgil Percec (pages xxi–xxii)

      Craig J. Hawker, E. W. “Bert” Meijer, Mitsuo Sawamoto and Karen L. Wooley

      Article first published online: 7 AUG 2008 | DOI: 10.1002/pola.22954

  2. Highlight

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    1. You have free access to this content
      The future of reversible addition fragmentation chain transfer polymerization (pages 5715–5723)

      Christopher Barner-Kowollik and Sébastien Perrier

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22866

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      In the current Highlight Article, we explore the future potential of the reversible addition fragmentation chain transfer (RAFT) process. Its current limitations are discussed alongside its many strengths. We identify future growths potentials and research opportunities. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Articles

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    1. Synthesis and LCST-type phase separation behavior in organic solvents of poly(vinyl ethers) with pendant imidazolium or pyridinium salts (pages 5724–5733)

      Ken-Ichi Seno, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22881

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      LCST-type phase separation in organic solvent was achieved using a polymer with pendant imidazolium or pyridinium salts, ionic liquid-like moieties. Well-defined poly-(salts) was quantitatively prepared by reactions with corresponding imidazoles or pyridine and poly(2-chloroethyl vinyl ether) which was synthesized by living cationic polymerization. A chloroform solution of the homopolymer with butyl imidazolium salts exhibited reversible and sharp transition on heating. Sensitive phase separation was also observed in a nonsolvent, such as toluene, ethyl acetate, THF, containing a small amount of a good solvent, such as 1-butanol. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Thermosensitive and control release behavior of poly (N-isopropylacrylamide-co-acrylic acid) latex particles (pages 5734–5741)

      Chia-Fen Lee, Chia-Cheng Lin and Wen-Yen Chiu

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22887

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      The poly(N-isopropylacrylamide-co-acrylic acid) (poly (NIPAAm-AA)) copolymer latex particles (microgels) were synthesized by the method of soapless emulsion polymerization. The concentration of acrylic acid (AA) and crosslinking agent N,N′-methylenebisacrylamide (MBA) were important factors to influence the lower critical solution temperature (LCST) of poly(NIPAAm-AA) microgels. The poly(NIPAAm-AA) copolymer microgels were then used as a thermosensitive drug carrier to load caffeine. The effects of concentration of AA and crosslinking agent on the control release of caffeine were investigated. The relationship of morphology, swelling, and control release behavior of these thermosensitive microgels was established. A new scheme was proposed to interpret the control release of the microgels with different morphological structures.

    3. Large-scale synthesis of arborescent polystyrenes (pages 5742–5751)

      Abdul Munam and Mario Gauthier

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22889

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      Large polymer samples are sometimes required for physical characterization work, for example, for mechanical and rheological properties measurements. This is troublesome for dendritic polymers, because of the small scale of the reactions used to prepare most of these materials. Scale-up is now demonstrated for the synthesis of arborescent polystyrenes of generations G0–G2 incorporating either short (Mn ≈ 5000) or long (Mn ≈ 30,000) side chains. This illustrates the need to adjust the reaction conditions used when the scale of a dendritic graft polymer synthesis is increased from 10 to 100 g. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. A phosphorus-containing thermotropic liquid crystalline copolyester with low mesophase temperature and high flame retardance (pages 5752–5759)

      Cheng-Shou Zhao, Li Chen and Yu-Zhong Wang

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22890

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      A novel phosphorus-containing semi-flexible main chain thermotropic liquid crystalline copolyester (P-TLCP-FS) was synthesized by melting transesterification. P-TLCP-FS had inherent viscosities of 0.92–1.12 dL/g and exhibited low and wide mesophase temperatures, ranging from 185 to 330 °C, which can match with the processing temperatures of most conventional polymers and high flame retardancy with a limiting oxygen index value of 70% and UL-94 V-0 rating. It can find its wide applications in preparing polymeric materials whose flame retardancy and mechanical properties can be improved simultaneously. Here x, 1-x, Y, Z, and 1-Y-Z denote the overall composition, not the block length.

    5. Photoreactive main chain liquid crystalline polyesters containing oxadiazole and bis(benzylidene) cycloalkanone units (pages 5760–5775)

      Rathinam Balamurugan and Palaninathan Kannan

      Article first published online: 25 JUL 2008 | DOI: 10.1002/pola.22891

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      Photo-reactive liquid crystalline polyesters containing oxadiazole and bis(benzylidene)cycloalkanone moieties were synthesized and characterized by structural, thermal, mesomorphic and optical measurements. The bis(benzylidene) cycloalkanone chromophores in the main chain can constitute both as a mesogen and photo-reactive centre while 1,3,4-oxadiazole is a well known fluorophore. HOPM investigations displayed enantiotropic nematic liquid crystalline phases and development of grainy to schlieren textures depends on the length of flexible spacer. Both photoisomerization and photodimerization are observed from the absorption spectra and discussed. The fluorescence spectra in solution state at various concentrations showed blue-emission maxima and the Stokes shifts being 48–49 nm. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Synthesis and characterization of novel polybenzimidazoles bearing pendant phenoxyamine groups (pages 5776–5793)

      Mahesh Kulkarni, Ravindra Potrekar, R. A. Kulkarni and S. P. Vernekar

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22892

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      Polybenzimidazoles tethered with various content of pendant phenoxy amine groups, synthesized by the condensation of 3,3'-diaminobenzidine with a mixture of new aromatic diacid, 3,5-dicarboxyl-4'-amino diphenyl ether, and isophthalic acid in different ratio were characterized by different instrumental techniques (FT-IR, TGA, DSC, XRD etc.) and for solvent solubility, mechanical properties and inherent viscosity. These polymers have high thermal stability with initial decomposition temperature 475–506 °C in nitrogen, high glass transition temperatures (Tg) ranging from 313–435 °C and good tensile strength in the range of 58 to 125 MPa. The suitability of these polymers for the application as polymer electrolyte for fuel cell at high temperature on doping with H3PO4 is revealed by their high proton conductivity in the range of 10−3 to 10−2 S/cm.

    7. Chemical modification and characterization of gigaporous polystyrene microspheres as rapid separation of proteins base supports (pages 5794–5804)

      Jian-Bo Qu, Wei-Qing Zhou, Wei Wei, Zhi-Guo Su and Guang-Hui Ma

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22893

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      The gigaporous polystyrene microspheres have two sets of pores: diffusion pores and through pores. They have great potentials in quick separation of proteins as chromatographic supports after hydrophilic modification. How to obtain stable hydrophilic coatings onto polystyrene materials is a booming interest in recent years. In this study, the gigaporous polystyrene microspheres surfaces became hydrophilic, biocompatible, and easy to be derivatized by classical methods after modified with PVA. Consequently, the nonspecific adsorption of proteins on these modified microspheres was significantly decreased. After further derivation, the coated gigaporous base supports could apply in various modes of high-speed protein chromatography. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. A strategy for synthesis of ion-bonded amphiphilic miktoarm star copolymers via supramolecular macro-RAFT agent (pages 5805–5815)

      Dairen Lu, Yun Wang, Tianyuan Wu, Kang Tao, Lijia An and Ruke Bai

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22894

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      Ion-bonded (polystyrene)2-poly(N-isopropylacrylamide)2, (PSt)2-(PNIPAM)2, was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) in the presence of the supramolecular macro-RAFT agent, ion-bonded (PSt)2-(DMP)2, where DMP refers to 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid. The obtained amphiphilic supramolecular miktoarm star polymer could be cleaved via the alteration of pH in solution at room temperature.

    9. Synthesis and properties of polyethylene with side-chain triphenylamines as hole-transporting materials (pages 5816–5825)

      Myung Hwan Park, Jung Oh Huh, Youngkyu Do and Min Hyung Lee

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22895

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      The copolymerization of ethylene with triphenylamine (TPA)-containing α-olefin monomer (1) using a rac-Et(Ind)2ZrCl2 (EBIZr)/MAO catalytic system efficiently provides a polyethylene with pendent TPA groups exhibiting high thermal stability and hole-transporting ability for the green emission of Alq3 when incorporated into the hole-transporting layer of an electroluminescence device.

    10. Photopatternable substrate-independent poly(glycidyl methacrylate-ran-2-(acryloyloxy) ethyl 2-methylacrylate) polymer films for immobilization of biomolecules (pages 5826–5838)

      Sean P. Cullen, Sangkeun Ha, Max G. Lagally and Padma Gopalan

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22896

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      We report the synthesis and characterization of a photocrosslinkable, patternable, and substrate-independent copolymer containing reactive epoxy groups for binding biomolecules. The epoxide-containing copolymer poly(glycidyl methacrylate-ran-2-(acryloyloxy) ethyl 2-methylacrylate) offers distinct advantages such as ease of application to various substrates, enhanced stability of the bound oligonucleotide, and low autofluorescence. The films are stable in water, tetrahydrofuran, and acetone for 4 months when spin-coated on glass, silicon wafers, stainless steel, or polycarbonate sheet. There is a linear relationship between the film thickness and amount of oligonucleotide immobilized. The crosslinked films are able to maintain high fluorescence signals after long aqueous washing. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Effect of catalyst partitioning in Co(II) mediated catalytic chain transfer miniemulsion polymerization of methyl methacrylate (pages 5839–5849)

      Niels M. B. Smeets, Johan P. A. Heuts, Jan Meuldijk and Alex. M. van Herk

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22898

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      A simple mathematical equation is derived to quantify the effect of catalyst partitioning in catalytic chain transfer mediated miniemulsion polymerization of methyl methacrylate. The instantaneous degree of polymerization is strongly dependent on the phase ratio used for the polymerization. Experiments are in excellent agreement with results of the calculation.

    12. Improvement of thermal stability of sulfonated polyphosphazenes by introducing a self-crosslinkable group (pages 5850–5858)

      Hyeoncheol Song, Seung Cheol Lee, Hye Young Heo, Dong Il Kim, Dong-Hwal Lee, Ju Ho Lee and Ji Young Chang

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22900

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      Sulfonated aryloxy substituted polyphosphazenes having hydroxymethylphenoxy groups were prepared for proton exchange membrane application. The polymers were self-crosslinkable. Upon heating, the crosslinking reaction occurred between methylols and aromatic rings on the phosphazene backbone via an electrophilic aromatic substitution mechanism, under acidic conditions.

    13. Amphiphilic gradient copolymers containing fluorinated 2-phenyl-2-oxazolines: Microwave-assisted one-pot synthesis and self-assembly in water (pages 5859–5868)

      Matthias Lobert, Richard Hoogenboom, Charles-André Fustin, Jean-François Gohy and Ulrich S. Schubert

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22901

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      The one-step synthesis of 2-(m-difluorophenyl)-2-oxazoline and its use as a monomer for microwave-assisted statistical cationic ring-opening copolymerizations is reported. Well-defined amphiphilic gradient copolymers, as evidenced by the polymerization kinetics, were prepared using 2-ethyl-2-oxazoline as comonomer and methyl tosylate as initiator. The second part of this contribution focuses on a detailed study of the self-assembly of the copolymers in aqueous solution revealing self-assembly of the gradient copolymers into spherical micelles. To quantify the influence of the fluorine atoms and the monomer distribution on the self-assembly a comparative study with gradient copolymers of 2-phenyl-2-oxazoline and 2-ethyl-2-oxazoline was performed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Synthesis, pH- and temperature-induced micellization and gelation of doubly hydrophilic triblock copolymer of poly(N,N-dimethylamino-2-ethylmethacrylate)-b-poly(ethylene glycol)-b-poly(N,N-dimethylamino-2-ethylmethacrylate) in aqueous solutions (pages 5869–5878)

      Zhiping Peng, Guangzhao Li, Xinxing Liu and Zhen Tong

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22904

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      Triblock copolymer of poly(N,N-dimethylamino-2-ethylmethacrylate) and poly(ethylene glycol) (PDMAEMA-b-PEG-b-PDMAEMA) was synthesized via ATRP. Micellization and gelation in aqueous solution were found due to the transition of PDMAEMA block from hydrophilic to hydrophobic at pH 14 and high temperature. The micelles in the solution of 1 mg/mL aggregated when heated beyond 50 °C at pH 14. Gelation occurred in the solution of 25 wt % at pH 14 and 80 °C due to the hydrophobic aggregation of the PDMAEMA blocks. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Methacrylic acid and methyl methacrylate oligomers adsorbed to porous isotactic poly(methyl methacrylate) ultrathin films and mechanistic studies of living template polymerization (pages 5879–5886)

      Hiroharu Ajiro, Daisuke Kamei and Mitsuru Akashi

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22905

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      The adsorption behaviors of methacrylic acid (MAA), methyl methacrylate (MMA), methacrylamide, and oligomers of MAA and MMA were examined toward porous isotactic-(it-) poly(methyl methacrylate) (PMMA) ultrathin films, as a model of active radical species in living template polymerization. The apparent predominant adsorption of oligomers to monomers was observed, suggesting that the mechanism of template polymerization follows the pick up mechanism. Adsorbed amounts were limited to about 5% and 15% at 0.1 mol L−1, respectively, which are much smaller values than corresponding st-polymers. The results imply that template polymerization in porous ultrathin film proceeds living manner. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Synthesis, morphology, and properties of hydroxyl terminated-POSS/polyimide low-k nanocomposite films (pages 5887–5896)

      Md Abdul Wahab, Khine Yi Mya and Chaobin He

      Article first published online: 28 JUL 2008 | DOI: 10.1002/pola.22906

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      Allyl alcohol terminated polyhedral oligomeric silsesquioxane (POSS-OH) structures possessing a high degree of functional groups on its surface have been synthesized and characterized. The use of nanoscale POSS-OH building materials were enable to improve thermo-mechanical properties due to the molecular scale and homogeneous distribution of POSS-OH particles in the matrix and also allow the development of low-k nancomposite materials. These novel POSS-OH materials were envisioned to function both as siloxane-reinforcing agents to add strength to the cured polymer matrix for enhancing properties. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Polyurethane–oligo(phenylenevinylene) random copolymers: π-Conjugated pores, vesicles, and nanospheres via solvent-induced self-organization (pages 5897–5915)

      P. Deepa and M. Jayakannan

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22907

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      A new series of polyurethane–oligo(phenylenevinylene) (OPV) random copolymers and nano-materials such as pores, vesicles, and luminescent spheres was reported. The π-conjugated segmented polymers were subjected to solvent- induced self-organization in THF or THF+water to produce a variety of morphologies. The mechanistic aspects of the self-organization process were studied using solution FT-IR and photophysical techniques, such as absorption and emission, to trace the factors thatwhich control the morphology. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Dendrimer-like miktoarm star terpolymers: A3-(B-C)3 via click reaction strategy (pages 5916–5928)

      Ozcan Altintas, A. Levent Demirel, Gurkan Hizal and Umit Tunca

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22908

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      Two samples of dendrimer-like miktoarm star terpolymers: (poly(tert-butyl acrylate))3-(polystyrene-poly (ε-caprolactone))3 (PtBA)3-(PS-PCL)3 and (PS)3-(PtBA-poly(ethylene glycol)3 were prepared using efficient Cu catalyzed Huisgen cycloaddition (click reaction). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Emulsion and controlled miniemulsion polymerization of the renewable monomer γ-methyl-α-methylene-γ-butyrolactone (pages 5929–5944)

      Genggeng Qi, Michael Nolan, F. Joseph Schork and Christopher W. Jones

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22909

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      Narrowly distributed copolymers of styrene and γ-methyl-α-methylene-γ-butyrolactone (MeMBL) were synthesized via RAFT miniemulsion and RAFT bulk polymerization with good control. The molecular weight of the copolymers increased linearly with the conversion while the polydispersity of the copolymers deceased with the conversion. Homopolymerization of MeMBL in (mini)emulsion is also reported.

    20. Synthesis, characterization, and optoelectronic properties of hyperbranched polyfluorenes containing pendant benzylether dendrons (pages 5945–5958)

      Lin-Ren Tsai, Chia-Wei Li and Yun Chen

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22910

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      New hyperbranched polyfluorenes (PHG0, PHG1) were prepared to investigate the structural effect on optoelectronic properties. The excimer emission of polyfluorene at about 530 nm was completely suppressed by the hyperbranched structure. The optoelectronic performance of the EL devices was strongly dependent upon chemical structures of the emitting polyfluorenes. The hyperbranched PHG0 with zero generation of benzylether side groups revealed the best device performance, with maximal luminance and maximal luminance efficiency of 2350 cd/m2 and 0.33 cd/A, respectively.

    21. Fixation of carbon dioxide into aliphatic polycarbonate, cobalt porphyrin catalyzed regio-specific poly(propylene carbonate) with high molecular weight (pages 5959–5967)

      Yusheng Qin, Xianhong Wang, Suobo Zhang, Xiaojiang Zhao and Fosong Wang

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22911

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      Cobalt porphyrin complex (TPPCoIIIX) (TPP = 5, 10, 15, 20-Tetraphenyl-porphyrin; X = halide) in combination with ionic organic ammonium salt was used for the regio-specific copolymerization of propylene oxide and carbon dioxide. Regio-regular poly(propylene carbonate) with head-to-tail linkage of 93% was obtained, and byproduct cyclic carbonate was successfully controlled to below 1%. Two active centers were suggested, which propagated simultaneously from either side of the cobalt porphyrin plane, leading to bimodal GPC profile of PPC. Additionally, by prolonging reaction time, PPC with head-to-tail linkage over 90% and Mn of 115 kg/mol was prepared, which exhibited glass transition temperature of 44.5 °C.

    22. Fabrication of monodisperse luminescent nanoparticles with core/shell poly(styrene/thiophene) structure (pages 5968–5975)

      Yeon Jae Jung, Sun Jong Lee, Sung Wook Choi and Jung Hyun Kim

      Article first published online: 29 JUL 2008 | DOI: 10.1002/pola.22912

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      Luminescent poly(styrene/thiophene) (PSt/PT) core/shell nanoparticles were prepared by oxidative polymerization in the presence of PSt seed particles. The formation of the PT shell resulted from the interface-dominant polymerization induced by electrostatic attraction between the sulfonate (SO3) group of anionic surfactant and Fe3+ ions. The total particle size and the thickness of the PT shell layer were controlled by changing the size of the template PSt nanoparticles, the concentration of the particles, and the same amount of monomer.

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