Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 18

15 September 2006

Volume 44, Issue 18

Pages 5237–5444

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. Copolymerization of norbornene and styrene catalyzed by a novel anilido–imino nickel complex/methylaluminoxane system (pages 5237–5246)

      Haiyang Gao, Yan Chen, Fangming Zhu and Qing Wu

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21651

      Thumbnail image of graphical abstract

      Copolymerizations of norbornene and styrene were carried out with a catalytic system of anilido–imino nickel complex (ArN[DOUBLE BOND]CHC6H4NAr)NiBr (Ar = 2,6-dimethylphenyl) and methylaluminoxane. NMR analysis of the end group of the copolymer with a low molecular weight confirmed that the active species was Ni[BOND]H, and the chain was initiated through a styrene secondary insertion or a norbornene 2,3-insertion into Ni[BOND]H and terminated mainly through β-H elimination from an inserted styrene unit.

    2. Direct dehydration polycondensation of lactic acid catalyzed by water-stable Lewis acids (pages 5247–5253)

      Akinori Takasu, Yuuki Narukawa and Tadamichi Hirabayashi

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21639

      Thumbnail image of graphical abstract

      Results of this study show that scandium trifluoromethanesulfonate [Sc(OTf)3] and scandium trifluoromethanesulfon imide [Sc(NTf2)3] are effective for one-step dehydration polycondensation of L-lactic acid. Bulk polycondensation of L-lactic acid was carried out at 130–170 °C to give PLLA with Mn of 5.1 × 104 to 7.3 × 104 (yield 32–60%). The solution polycondensation was performed at 135 °C for 48 h to afford PLLA with Mn of 1.1 × 104 with good yield (90%). In no case did 1H NMR, specific optical rotation, or DSC measurement confirm racemizations. The catalyst was recovered easily by extraction with water and reused for polycondensation.

    3. Synthesis and characterization of novel fully aliphatic polyimidosiloxanes based on alicyclic or adamantyl diamines (pages 5254–5270)

      Anu Stella Mathews, Il Kim and Chang-Sik Ha

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21636

      Thumbnail image of graphical abstract

      A series of novel fully aliphatic polyimidosiloxanes were prepared by high temperature one-step synthesis in m-cresol. 1,3-bis (3-amino propyl)-tetra methyl disiloxane and alycyclic bis cyclohexane or adamantane diamines were copolymerized with alicyclic diahydride to give the corresponding polyimides. The resulting polymers showed high transparency, low dielectric constant, and good solubility together with high thermal and mechanical properties, which can be attributed to balance of stiffness, polarity, free volume, flexibility, and silicon content of backbone units. Adamantane moieties in the backbone of polyimidosiloxanes further increased the transparency, solubility, glass transition temperature and lowered the dielectric constant.

    4. Synthesis and properties of new photosensitive triazene polyacrylates (pages 5271–5282)

      Emil C. Buruiana, Tinca Buruiana, Hahui Lenuta, Thomas Lippert, Lukas Urech and A. Wokaun

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21653

      Thumbnail image of graphical abstract

      We report the first synthesis of triazene acrylic monomers, 1-(phenyl)-3-(2 acryloyloxyethyl)-3-methyl triazene-1 and 1-(p-nitrophenyl)-3-(2 acryloyloxyethyl)-3-methyl triazene-1, and their copolymerization tendency with methyl methacrylate to induce ablative properties to the resulting polymers. Depending on the nature of the triazene substituent, some features of the ultraviolet/laser ablation process have been revealed.

    5. Synthesis and characterization of conducting polythiophene/carbon nanotubes composites (pages 5283–5290)

      Mohammad Rezaul Karim, Chul Jae Lee and Mu Sang Lee

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21640

      Thumbnail image of graphical abstract

      Conducting polythiophene coated onto single-wall carbon nanotube composites was synthesized by the in situ chemical oxidative polymerization method. The resulting cablelike material of single-wall carbon nanotubes coated by conducting polythiophene (60–80 nm in diameter) showed a new morphological structure with various enhanced physical properties, including thermal and electrical properties. The improvements made in the various properties of these composites are expected to enhance their application potential in the fields of light-emitting diodes, electrochromic and photovoltaic devices, and sensors.

    6. Photoinitiated polymerization in bicontinuous microemulsions: Fluorescence monitoring (pages 5291–5303)

      C. Peinado, P. Bosch, V. Martín and T. Corrales

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21649

      Thumbnail image of graphical abstract

      Fluorescence methodology has been applied to monitor the photopolymerization of bicontinuous microemulsions. The fluorescence intensity ratio for a given value of the conversion is higher in microemulsions containing sodium dodecyl sulfate as a surfactant than those containing cetyltrimethylammonium bromide. This confirms that the crosslink density does not develop equivalently as a function of conversion and agrees well with the morphology of the polymerized mesoporous solids. Higher fluorescence intensity is associated with a more rigid microenvironment because of faster phase separation of the polymerizing domain, smaller pores, and poorest pore connectivity.

    7. Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate (pages 5304–5315)

      Rodrigo París and José Luis de la Fuente

      Version of Record online: 2 AUG 2006 | DOI: 10.1002/pola.21631

      Thumbnail image of graphical abstract

      Functional copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The copolymer composition, demonstrating the gradient character, and the microstructure were analyzed with nuclear magnetic resonance. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33.

    8. Elaboration of well-defined Rasta resins and their use as supported catalytic systems for atom transfer radical polymerization (pages 5316–5328)

      David Fournier, Sagrario Pascual, Véronique Montembault and Laurent Fontaine

      Version of Record online: 7 AUG 2006 | DOI: 10.1002/pola.21644

      Thumbnail image of graphical abstract

      New supported catalytic systems based on the immobilization of a ligand onto supported (co)polymers were prepared, allowing copper immobilization onto a solid support during the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The supported catalysts were elaborated by the ATRP of 2-vinyl-4,4-dimethyl-5-oxazolone and/or styrene onto a Wang resin initiator. The best results were obtained with the supported ATRP of styrene followed by the nucleophilic substitution of bromine by N,N,N′,N′-tetraethyldiethylenetriamine (Wang-g-polystyrene–N,N,N′,N′-tetraethyldiethylenetriamine) at the chain end of the grafted polystyrene chains. The supported complexes mediated a controlled polymerization of MMA, yielding polymers with controlled molar masses and low polydispersity indices. Moreover, after the polymerization, 96% of the initial copper was kept in the beads.

    9. Crosslinkable poly(propylene carbonate): High-yield synthesis and performance improvement (pages 5329–5336)

      Youhua Tao, Xianhong Wang, Xiaojiang Zhao, Ji Li and Fosong Wang

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21595

      Thumbnail image of graphical abstract

      A crosslinking strategy was used to improve the thermal and mechanical performance of poly(propylene carbonate) (PPC): PPC bearing a small moiety of pendant C[DOUBLE BOND]C groups was synthesized by the terpolymerization of allyl glycidyl ether (AGE), propylene oxide (PO), and carbon dioxide (CO2). Almost no yield loss was found in comparison with that of the PO and CO2 copolymer when the concentration of AGE units in the terpolymer was less than 5 mol %. Once subjected to UV-radiation crosslinking, the crosslinked PPC film showed an elastic modulus 1 order of magnitude higher than that of the uncrosslinked one. Therefore, the PPC application window was enlarged to include a higher temperature zone by the crosslinking strategy.

    10. Ring-opening metathesis polymerization of amino acid-functionalized norbornene derivatives (pages 5337–5343)

      Sutthira Sutthasupa, Kayo Terada, Fumio Sanda and Toshio Masuda

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21580

      Thumbnail image of graphical abstract

      Amino acid-derived novel norbornene derivatives (NBA, NBL, and NBF) were synthesized and polymerized using the Grubbs 2nd generation ruthenium catalyst. Although NBA, NBL, and NBF did not undergo homopolymerization, they underwent copolymerization with NB to give the copolymers with Mn ranging from 5200 to 38,100. The maximum incorporation ratio of the amino acid-based unit was 9%, and the cis contents of the main chain were 54–66%.

    11. Cyclic and telechelic ladder polymers derived from tetrahydroxytetramethylspirobisindane and 1,4-dicyanotetrafluorobenzene (pages 5344–5352)

      Hans R. Kricheldorf, Nino Lomadze, Detlev Fritsch and Gert Schwarz

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21627

      Thumbnail image of graphical abstract

      Polycondensations of 1,4-dicyanotetrafluorobenzene with 5,5,6,6-tetrahydroxyspirobisindane, promoted by potassium carbonate, yielded under optimized reaction conditions cyclic ladder polymers. The addition of difunctional end-capping agents and higher concentrations yielded linear polymers.

    12. Preparation and characterization of chitosan-graft-poly (ϵ-caprolactone) with an organic catalyst (pages 5353–5361)

      Hao Feng and Chang-Ming Dong

      Version of Record online: 7 AUG 2006 | DOI: 10.1002/pola.21625

      Thumbnail image of graphical abstract

      Chitosan-graft-poly(ϵ-caprolactone) was prepared via the ring-opening graft polymerization of ϵ-caprolactone through chitosan with 4-dimethylaminopyridine as a catalyst and water as a swelling agent. The selective N-substitution of ϵ-caprolactone to chitosan occurred under the reaction conditions used, and the percentage of amino groups initiating the graft polymerization decreased with an increasing feed ratio of ϵ-caprolactone to chitosan. Consequently, it is promising to combine the bioactive functions of chitosan with the mechanical properties of biodegradable biomaterials to generate new biohybrids without toxic metal.

    13. Vinyl copolymers containing pendant 1,4-distyrylbenzene and 1,3,4-oxadiazole chromophores: Preparation and optoelectronic properties (pages 5362–5377)

      Kun-Ming Yeh and Yun Chen

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21592

      Thumbnail image of graphical abstract

      Two vinyl (P1, P2) and two main chain copolymers (P3, P4) containing distyrylbenzene and oxadiazole derivatives were prepared. The architecture of P1 prevented intermolecular interaction. The main emitter was distyrylbenzene fluorophore (ca. 450 nm) in blend of P1 and P2 owing to efficient energy transfer. The blend exhibited three kinds of redox behavior depending on their weight ratios. The luminance and efficiency of the EL device (ITO/PEDOT/MEH-PPV+P2/Al) were improved to 1285 cd/m2 and 0.44 cd/A, respectively, at 20 wt % of P2.

    14. Electroluminescence from a conjugated polymer grafted with CdSe/ZnS: High brightness and improved efficiency (pages 5378–5390)

      Kuei-Bai Chen, Ming-Hwey Chen, Sheng-Hsiung Yang, Chao-Hsiang Hsieh, Chain-Shu Hsu, Chia-Chun Chen and Hsiao-Ju Chien

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21608

      Thumbnail image of graphical abstract

      A novel light-emitting material, CdSe/ZnS quantum dot encapsulated with a sulfide-containing conjugated polymer S-PPV, showed a bright yellow emission. A double-layer device using S1PPVCdSe as active layer showed a maximum luminescence of 15960 cd/m2 and a current yield of 1.47 cd/A.

    15. Synthesis and properties of low-dielectric-constant polyimides with introduced reactive fluorine polyhedral oligomeric silsesquioxanes (pages 5391–5402)

      Yun-Sheng Ye, Wen-Yi Chen and Yen-Zen Wang

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21650

      Thumbnail image of graphical abstract

      In this investigation, a novel reactive polyhedral oligomeric silsesquioxane (POSS) containing fluorine atoms was successfully synthesized. The reactive fluorine POSS [octakis(dimethylsiloxyhexafluoropropylglycidyl ether)silsesquioxane (OFG)] was able to cure with poly(amic acid) to form a curing framework for a polyimide nanocomposite via curing and imidization. Because of the curing structure and the fluorine atoms and nanoporous structure of OFG, this polyimide nanocomposite possessed higher thermal properties and a lower dielectric constant than other polyimides. Furthermore, surface properties were introduced to calculate the hydrophobicity and polarizability of the polyimides.

    16. Synthesis and characterization of a π-conjugated hybrid of oligothiophene and porphyrin (pages 5403–5412)

      Kenichi Oyaizu, Manabu Hoshino, Masuhide Ishikawa, Takuya Imai and Makoto Yuasa

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21596

      Thumbnail image of graphical abstract

      Oxidative polymerization of 5-(3-thienyl)-10,15,20-triethyl-21H,23H-porphine gave a novel oligomeric porphyrin linked at the 2,5-positions of the thienyl group. Electric conductivity after I2 doping indicated that the oligomer had a π-conjugated structure with a delocalization of π electrons over the thienylene backbone. Calculations revealed a low HOCO-LUCO gap. Regioregular (head-to-tail) structure was inferred from spectroscopic and calculational results. The pendant porphyrin groups formed a regular J-type array along the thienylene backbone.

    17. Preparation and characterization of MPEG–PCL diblock copolymers with thermo-responsive sol–gel–sol phase transition (pages 5413–5423)

      Moon Suk Kim, Hoon Hyun, Kwang Su Seo, Young Ho Cho, Jung Won Lee, Chang Rae Lee, Gilson Khang and Hai Bang Lee

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21659

      Thumbnail image of graphical abstract

      MPEG-PCL diblock copolymer solution exhibits a sol–gel–sol transition as a function of temperature. Thermo-responsible materials in this work could utilize as a potential injectable drug carrier.

    18. Para-linked and meta-linked cationic water-soluble fluorene-containing poly(aryleneethynylene)s: Conformational changes and their effects on iron–sulfur protein detection (pages 5424–5437)

      Yan-Qin Huang, Qu-Li Fan, Sheng-Biao Li, Xiao-Mei Lu, Fan Cheng, Guang-Wei Zhang, Yi Chen, Lian-Hui Wang and Wei Huang

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21591

      Thumbnail image of graphical abstract

      Four cationic water-soluble fluorene-containing poly(aryleneethynylene)s (PAEs) were synthesized. P1′–P3′ were described as PxMy+ polymers (P100Mmath image, P50Mmath image, and P0Mmath image), where the subscript in Px and My respectively correspond to the percentage of para and meta units in the polymer structure. P4′ had an analogous backbone to P3′ except for a cationic side chain on the meta-phenylene unit. With gradually increased meta-phenylene content in these PAE backbones, a gradual transition process of self-assembly from disordered aggregate structure to helical structure was observed in water. The effects of their conformational changes on iron–sulfur protein detection were also reported.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. You have free access to this content
      Synthesis and characterization of a novel ABA triblock copolymer via 4,4′-bis(trifluorovinyloxy)biphenyl and methyl methacrylate (pages 5438–5444)

      Guolin Lu, Sen Zhang and Xiaoyu Huang

      Version of Record online: 9 AUG 2006 | DOI: 10.1002/pola.21648

      Thumbnail image of graphical abstract

      A macroinitiator with two atom transfer radical polymerization initiation groups at both ends was prepared by the thermal step-growth cycloaddition polymerization of 4,4′-bis(trifluorovinyloxy)biphenyl and was followed by a reaction with 2-bromo-1-(4-trifluorovinyloxyphenyl)-propan-1-one. Next, the atom transfer radical polymerization of methyl methacrylate was initiated by the macroinitiator to obtain the ABA triblock copolymer [A = poly(methyl methacrylate) block; B = perfluorocyclobutyl aromatic ether based fluoropolymer block). The copolymer showed excellent solubility in conventional solvents.