Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 5

1 March 2009

Volume 47, Issue 5

Pages 1237–1483

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. A general strategy for highly efficient nanoparticle dispersing agents based on hybrid dendritic linear block copolymers (pages 1237–1258)

      Robert Vestberg, Ashley M. Piekarski, Eric D. Pressly, Kim Y. Van Berkel, Michael Malkoch, Jeffrey Gerbac, Nobuhiko Ueno and Craig J. Hawker

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23186

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      A modular approach to the synthesis of a library of hybrid dendritic-linear copolymers was developed and by accurately controlling the molecular weight of the linear block, generation number of the dendrimer and the nature of the dendritic chains ends, the performance of these hybrid block copolymers as dispersing agents was optimized for a range of nanoparticles. For titanium dioxide nanoparticles, dispersion in a poly(methyl methacrylate) matrix was maximized with a second generation dendrimer containing 4 carboxylic acid end groups and the quality of dispersion was observed to be superior to commercial dispersing agents for TiO2. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Hydrobromination of residual vinyl groups on divinylbenzene polymer particles followed by atom transfer radical surface graft polymerization (pages 1259–1265)

      Fredrik Limé and Knut Irgum

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23209

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      The pendant vinyl groups on cross-linked divinylbenzene particles were subjected to hydrobromination. By having bromine in the primary position on the alkyl chain, the particles could be used as macroinitiators for atom transfer radical surface graft polymerization. Glycidyl methacrylate was subsequently grafted from the surface of the particles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Water-soluble polymers from acid-functionalized norbornenes (pages 1266–1273)

      Karen Lienkamp, Christoph F. Kins, Sterling F. Alfred, Ahmad E. Madkour and Gregory N. Tew

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23223

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      ROMP-based diacids were successfully prepared within the assistance of protecting group chemistry. Their solution properties were characterized by light scattering as a function of pH. A dimensional transition was observed from greater than 15 nm to less than 10 nm as the pH was varied from 11 to 3. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Synthesis of high-molecular-weight linear methacrylate copolymers with spiropyran side groups: Conformational changes of single molecules in solution and on surfaces (pages 1274–1283)

      Ronald Adelmann, Petra Mela, Marat O. Gallyamov, Helmut Keul and Martin Möller

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23230

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      UV-induced conformational changes of P(BMA-co-HEMA-spiropyran) were studied. The rate constants and half-life times of the ring-closure reaction from zwitterionic merocyanine to the spiropyran species were determined in the presence and absence of mica-dispersed particles in toluene both for the free spiropyran and the polymer-bound spiropyran. Scanning force microscopy was used to visualize the conformation of spiropyran-decorated single macromolecular chains and agglomerated polymer-bound merocyanine adsorbed on mica.

    5. Amphiphilic conetworks. IV. Poly(methacrylic acid)-l-polyisobutylene and poly(acrylic acid)-l-polyisobutylene based hydrogels prepared by two-step polymer procedure. New pH responsive conetworks (pages 1284–1291)

      Ludĕk Toman, Miroslav Janata, Jiří Spĕváček, Jiří Brus, Antonín Sikora, Jiří Horský, Petr Vlček and Petra Látalová

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23234

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      Amphiphilic polymer conetworks consisting of poly(methacrylic acid) (PMAA) or poly(acrylic acid) (PAA) and polyisobutylene (PIB) chains were prepared by two-step polymer synthesis. Isobutylene (IB) was copolymerized with 3-isopropenyl-α,α-dimethylbenzyl isocyanate (IDI) cationically giving the IB-IDI random copolymer with pendant isocyanate groups along the chain, PIB(NCO)n. The isocyanate groups of the copolymer were transformed in situ to methacrylate (MA) groups by the reaction with 2-hydroxyethyl methacrylate (HEMA). Resulting PIB(MA)n was copolymerized radically with methacrylic or acrylic acid giving rise to PMAA-l-PIB and PAA-l-PIB conetworks.

    6. Poly(ether tert-amine): A novel family of multiresponsive polymer (pages 1292–1297)

      Yanrong Ren, Xuesong Jiang and Jie Yin

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23235

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      A novel multi-responsive poly(ether tert-amine) (PEA), were synthesized by nucleophi lic addition/ring-opening reaction of commercial poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO) di-epoxy and di-amine monomer. These PEAs exhibit very sharp response to temperature, pH and ionic strength, with adjustable and sharp phase transitions in the range of 27–100 °C, and will be very potential in applications of drug delivery, separation and biotechnology.

    7. The study of electroactive block copolymer containing aniline pentamer isolated from different solvents (pages 1298–1307)

      Jun Hu, Lihong Huang, Le Lang, Yadong Liu, Xiuli Zhuang, Xuesi Chen, Yen Wei and Xiabin Jing

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23236

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      A triblock copolymer, mPEG2k-aniline pentamer-mPEG2k, was used as one model to investigate the arrangement–solvent relationship. The crystalline properties of mPEG blocks in powder prepared from different solvents differed obviously, which was affected by the morphologies of copolymer in these solvents. The copolymer self-assembled into spherical micelles in toluene and into lamellar crystals in water and THF. From the SAXS results, the AP blocks showed different arrangement in the powder prepared from different solvents. More importantly, the change in the AP arrangement showed a similar tendency to the changes of the morphologies of copolymer, the Xc and Tc of mPEG blocks, and the polarity and solubility of solvents. From the selected solvents, the ones with higher polarity and better solubility induced more regular arrangement of AP blocks, which may be useful for choosing solvents for the preparation of higher conductivity polymers' films containing aniline oligomers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Synthesis and characterization of star graft copolymers with asymmetric mixed “V-shaped” side chains via “click” chemistry on a hyperbranched polyglycerol core (pages 1308–1316)

      Guowei Wang, Chao Liu, Mugang Pan and Junlian Huang

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23238

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      The star graft copolymers with well-defined asymmetric mixed “V-shaped” side chains of two identical polystyrene, poly(tert-butyl acrylate) using the hypberbranched polyglycerol as core were synthesized via the “click” chemistry. The final products and intermediates were characterized in details. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Pyrene functional poly(vinyl alcohol) by “click” chemistry (pages 1317–1326)

      Bahadir N. Gacal, Banu Koz, Burcin Gacal, Baris Kiskan, Matem Erdogan and Yusuf Yagci

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23240

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      Side-chain pyrene functional poly(vinyl alcohol) (PVA) was synthesized by using “click chemistry” strategy. First, partial tosylation of PVA with p-toluene sulphonyl chloride were performed. The resulting PVA-Ts polymer was then quantitatively converted into poly(vinyl alcohol)-azide (PVA-N3) in the presence of NaN3/DMF at 60 °C. Propargyl pyrene was prepared independently as a photoactive click component. Finally, azido functionalized PVA was coupled to propargyl pyrene with high efficiency by click chemistry. Incorporation of pyrene functionality in the resulting polymer was confirmed by spectral analysis. It is also shown that pyrene functionalized PVA (PVA-Py) exhibited characteristic fluorescence properties and improved solubility in highly polar solvents such as water, DMSO, and DMF as well as less polar solvent such as THF compared with pristine PVA.

    10. PCPP derivatives containing carbazole pendant as hole transporting moiety for efficient blue electroluminescence (pages 1327–1342)

      Jinwoo Kim, Youngeup Jin, Jaehong Kim, Jaeyeon Jung, Sun Hee Kim, Kwanghee Lee and Hongsuk Suh

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23241

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      The conjugated copolymers of BCzPh-PCPPs and CzPh-PCPPs with carbazole pendant were synthesized by Suzuki reaction. The carbazole moiety, which can improve the hole injection ability, was introduced as a pendant on the PCPP backbone. Their thermal, electrochemical, photoluminescent, and electroluminescent properties were investigated.

    11. Mn2(CO)10-induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments (pages 1343–1353)

      Kazuhiko Koumura, Kotaro Satoh and Masami Kamigaito

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23243

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      The controlled/living radical copolymerization of vinyl acetate (VAc) and methyl acrylate (MA) was investigated using manganese complex [Mn2(CO)10] in conjunction with an alkyl iodide (R–I) as an initiator under weak visible light. The R–I/Mn2(CO)10 system was effective for the copolymerization of MA and VAc, in which MA was consumed faster than VAc, and then the remaining VAc was continuously and quantitatively consumed after the complete consumption of MA. The 1H and 13C NMR analyses revealed that the obtained products are block copolymers consisting of gradient MA/VAc segments, in which the VAc content gradually increases, and homopoly(VAc). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Growth of lightly crosslinked PHEMA brushes and capsule formation using pickering emulsion interface-initiated ATRP (pages 1354–1367)

      Yunhua Chen, Chaoyang Wang, Jianxin Chen, Xinxing Liu and Zhen Tong

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23244

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      Initiator-immobilized silica nanoparticles assembled at the interface of paraffin oil-in-water Pickering emulsions. Pickering emulsion interface-initiated atom transfer radical polymerization (PEII-ATRP) was conducted in the water phase of Pickering emulsions from the part of the surfaces of initiator-immobilized silica nanoparticles exposed to water. Hollow hybrid capsules were formed because of growth of lightly crosslinked PHEMA brushes. Novel hybrid capsules (“colloidosomes”) with semipermeability can be further utilized to develop microdevices for drugs or cells delivery. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. All-aromatic liquid crystalline thermosets with high glass transition temperatures (pages 1368–1380)

      Mazhar Iqbal, Ben Norder, Eduardo Mendes and Theo J. Dingemans

      Version of Record online: 22 JAN 2009 | DOI: 10.1002/pola.23245

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      We have synthesized a new family of all-aromatic liquid crystal oligomers with reactive phenylethynyl end groups. All ester-based oligomers can easily be processed from the melt, and after cure the nematic thermosets display physical and mechanical properties superior to PPS, PEEK, or PEKK. Depending on the backbone composition, we can synthesize thermosets with Tgs in the range of 164–275 °C and high storage moduli at elevated temperature (∼ 2 GPa at 200 °C). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Linking polythiophene chains with vinylene-bridges: A way to improve charge transport in polymer field-effect transistors (pages 1381–1392)

      Kun Lu, Xiangnan Sun, Yunqi Liu, Chongan Di, Hongxia Xi, Gui Yu, Xike Gao and Chunyan Du

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23246

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      A series of branched polythiophene derivatives with different densities of vinylene-bridges as linking chains were designed and synthesized. Organic field-effect transistors based on them were fabricated and characterized, which were found to exhibit excellent p-type OFET properties. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Emulsion polymerization of ethylene from mesoporous silica nanoparticles with vinyl functionalized monolayers (pages 1393–1402)

      Liangming Wei and Yafei Zhang

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23247

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      A stable vinyl functionalized mesoporous silica nanoparticles (V-MSNs)/PE nanocomposite latex was synthesized via emulsion polymerization of ethylene from V-MSNs. Because of a strong interaction between PE and V-MSNs, a stable PE shell/V-MSNs core structure was formed upon annealing this nanocomposite. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Free radical copolymerization of α-fluoroacrylates for optical materials: Synthesis and characterization (pages 1403–1411)

      Jean-Marc Cracowski, Véronique Montembault, Dominique Bosc, Bruno Améduri, Fabrice Odobel and Laurent Fontaine

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23249

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      2,2,2-Trifluoroethyl α-fluoroacrylate (FATRIFE) and 2,2,2-trichlororoethyl α-fluoroacrylate (FATRICE) copolymers were synthesized in good yields by radical process. The reactivity ratios have been measured to be rFATRIFE = 0.56 ± 0.01 and rFATRICE = 0.11 ± 0.01 at 74 °C. Thermal and optical properties of the resulting polymers were examined. The glass transition temperature of copolymers varied from 113 °C to 127 °C, increasing with the molar ratio of FATRICE. The refractive indices measured at 633, 1320, and 1550 nm have been found to vary linearly with the chlorine content of the copolymer, allowing a precise control of the refractive index.

    17. Preparation of glycopolymer-substituted gold nanoparticles and their molecular recognition (pages 1412–1421)

      Masayuki Toyoshima and Yoshiko Miura

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23250

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      Glycopolymer-substituted gold nanoparticles were prepared via living radical polymerization with a reversible addition-fragmentation chain transfer (RAFT) reagent. Polyacrylamide derivatives with saccharides were synthesized, and hydrogenated to obtain thiol-terminated polymer. The thiol-terminated glycopolymers were mixed with gold nanoparticles to yield the glycopolymer substituted gold nanoparticles, and the nanoparticle recognized proteins and bacterium. The molecular recognition abilities and solubilities of the gold nanoparticle were tuned by the polymerization. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Poly(N,N-dimethylacrylamide) hydrogels obtained by frontal polymerization (pages 1422–1428)

      Giuseppe Caria, Valeria Alzari, Orietta Monticelli, Daniele Nuvoli, Josè M. Kenny and Alberto Mariani

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23251

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      Poly(N,N-dimethylacrylamide) hydrogels were prepared by using frontal polymerization. By properly choosing the reaction conditions (presence and type of solvent, initiator concentration), materials having swelling capability in water ranging from 700 to 3500% were obtained. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Analysis of association constant for ground-state dye-electron acceptor complex of photoinitiator systems and the association constant effect on the kinetics of visible-light-induced polymerizations (pages 1429–1439)

      Dongkwan Kim, Alec B. Scranton and Jeffrey W. Stansbury

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23252

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      We suggested a new analysis model based on the Benesi–Hildebrand model to characterize both RB/DPI and FL/DPI photoinitiator systems to form 1:1 ground-state complexes in HEMA monomer. In addition, we investigated the effect of ground-state complex formation on the kinetics of visiblelight-induced polymerizations. The observed differences in the polymerization kinetics arise from the different values of the association constant of the ground-state dye-acceptor complex, which correlates with the back-electron transfer reaction. These results may allow better characterization of existing photoinitiators while providing useful information for the design of new and more efficient initiator systems.

    20. Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring-opening polymerization of glycolide (pages 1440–1449)

      Estelle Gautier, Patrick Fuertes, Philippe Cassagnau, Jean-Pierre Pascault and Etienne Fleury

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23253

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      Poly(glycolic acid) (PGA) with controlled molar masses ranged from 2000 to 42,000 g/mol were synthesized by ring-opening polymerization (ROP) of glycolide in melt conditions and in the presence of two different initiators: 1-dodecanol and 1,4-butanediol. Evolutions of thermal and rheological properties with molar mass of the polymer were established. By in situ polymerization of glycolide monomer between the plates of the rheometer, it was also possible to propose a kinetic modeling of the polymerization by inverse calculation. Such approach and few experimental data obtained are new and allow to better describe the melt ROP of glycolide and rheological properties of PGA.

    21. Synthesis of PEG-PNIPAM-PLys hetero-arm star polymer and its variation of thermo-responsibility after the formation of polyelectrolyte complex micelles with PAA (pages 1450–1462)

      Jian Li, Wei-Dong He, Ning He, Shou-Chen Han, Xiao-Li Sun, Li-Ying Li and Bo-Yu Zhang

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23254

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      Hetero-arm star terpolymer, PEG-PNIPAM-PLys, was synthesized by “clicking” the azide group at the junction point of PEG-b-PNIPAM with the alkyne end group of PLys. Surprisingly, PNIPAM arm in PEG-PNIPAM-PLys nearly loses temperature responsibility. However, PEG-PNIPAM-PLys can complex with poly(acrylic acid) to form stable core-shell polyelectrolyte complex micelles and PNIPAM shell is thermo- responsive.

    22. Synthesis and properties of sulfonated polyimides derived from bis(sulfophenoxy) benzidines (pages 1463–1477)

      Yoshiki Sutou, Yan Yin, Zhaoxia Hu, Shouwen Chen, Hidetoshi Kita, Ken-Ichi Okamoto, Hongyuan Wang and Hironobu Kawasato

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23123

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      A series of aromatic sulfonated polyimides (SPIs) bearing sulfophenoxy side groups were successfully synthesized and evaluated as polymer electrolyte membranes for fuel cell applications. The SPI membranes showed anisotropic membrane swelling in water with much larger dimensional change in thickness direction than in plane one. They showed the better proton-conducting performance, for example, of 0.05 S/cm at 50% RH and 120 °C. They showed much better water stability compared with the other SPI membranes reported so far. They showed high performance of polymer electrolyte fuel cells (PEFCs) at 90 °C and 84–30% RH, and have high potential for PEFC applications.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
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      ATRP Synthesis of poly(4-bromostyrene)-b-poly(propylene glycol) block copolymer and its self-assembly in catalystic emulsion polymerization to form luminescent nanospheres with core-shell structure (pages 1478–1483)

      Weizhi Z. Wang, Wenbin Song, Rui Wang and Tianxi X. Liu

      Version of Record online: 23 JAN 2009 | DOI: 10.1002/pola.23239

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      Poly(propylene glycol)-b-poly(4-bromostyrene) (PPG-b-PBS) block copolymers with different hydrophobicities have been synthesized by ATRP, which are used as micelle templates for the synthesis of nanostructured luminescent spheres by catalystic emulsion polymerizaton. The optical properties of the nanospheres can be tuned by adding 4,7-dibromo-2,1,3-benzothiadiazole (BTH) in emulsion polymerization process. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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