Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 7

1 April 2005

Volume 43, Issue 7

Pages 1317–1543

  1. Articles

    1. Top of page
    2. Articles
    1. Synthesis and second-order nonlinear optical properties of multifunctional polysiloxanes with sulfonyl-based chromophores (pages 1317–1324)

      Jianli Hua, Zhen Li, Kai Long, Jingui Qin, Shaojun Li, Cheng Ye and Zuhong Lu

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20595

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      Two new polysiloxanes (P1 and P2) with a high density of sulfonyl-based chromophores were prepared by a new two-step method. Their maximum absorptions were blueshifted about 42 and 8 nm, respectively, in comparison with those of the corresponding chromophores with a nitro acceptor and resulted in a wider transparency window. A poled film of P1 exhibited a resonant nonlinear optical coefficient (d33) of 16.2 pm/V.

    2. Synthesis of long-chain-branched polyethylene by ethylene homopolymerization with a novel nickel(II) α-diimine catalyst (pages 1325–1330)

      Hao Zou, Fang Ming Zhu, Qing Wu, Jiao Yan Ai and Shang An Lin

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20596

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      A novel nickel(II) α-diimine complex of 2,3-bis(2-phenylphenyl)butane diimine nickel dibromide ({[2-C6H4(C6H5)][BOND]N[DOUBLE BOND]C[BOND](CH3)C(CH3)[DOUBLE BOND]N[BOND][2-C6H4(C6H5)]}NiBr2) possessing potentially two stereoisomers (complexes a and b) was synthesized for the preparation of long-chain-branched polyethylene with a broad or bimodal molecular weight distribution in the presence of modified methylaluminoxane.

    3. Polyamide–polyester multiblock copolymers by chain-coupling reactions of carboxy-terminated polymers with phenylene and pyridylene bisoxazolines (pages 1331–1341)

      Laurent Néry, Hervé Lefebvre and Alain Fradet

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20602

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      Mixtures of carboxy-terminated oligomers were reacted in the bulk with arylene bisoxazolines to yield random multiblock copolymers that exhibited properties similar to those of alternating multiblock copolymers prepared in the conventional way. The advantages of the method were a much shorter reaction time, a lower temperature, and easy control of the copolymer properties through the starting oligomer mass ratio.

    4. Preparation and clinical application of immunomagnetic latex (pages 1342–1356)

      Ping-Cheih Wang, Chia-Fen Lee, Tai-Horng Young, Dong-Tsamn Lin and Wen-Yen Chiu

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20601

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      Magnetic poly(methyl methacrylate) (PMMA)/poly(methyl methacrylate-co-methacrylic acid) [P(MMA–MAA)] composite polymer latices were synthesized by two-stage soapless emulsion polymerization in the presence of magnetite (Fe3O4) ferrofluids. The Fe3O4/polymer particles were monodisperse, and the composite polymer particle size was approximately 100 nm. The morphology of the magnetic composite polymer latex particles was a core–shell structure. Antibodies (anti-human immunoglobulin G) were then chemically bound with COOH groups onto the surface of the magnetic core–shell composite latices through the medium of carbodiimide to form the antibody-coated magnetic latices (magnetic immunolatices). With a magnetic sorting device, the magnetic immunolatices derived from the magnetic PMMA/P(MMA–MAA) core–shell composite polymer latex performed well in the cell-separation experiments based on the antigen–antibody reaction.

    5. Pulsed laser polymerization study of the propagation kinetics of acrylamide in water (pages 1357–1368)

      Shane A. Seabrook, Matthew P. Tonge and Robert G. Gilbert

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20605

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      Pulsed laser polymerization (PLP) with size exclusion chromatography (SEC) was successfully applied to measure the propagation rate coefficient (kp) of the water-soluble monomer acrylamide (AAm). The apparent kp value depended on the monomer concentration and the initiator type and concentration. Arrhenius parameters were found for 0.32 M AAm over a range of 5–50 °C. The effect of changing the monomer concentration (solvent effect) was very similar to that observed for N-isopropylacrylamide and acrylic acid, with the apparent kp value decreasing with increasing monomer concentration. A simple model that accounted for dimer formation was able to account for this effect. However, a full understanding must include a description of the changes in the free energy of activation and other intermolecular interactions.

    6. Shape-memory polymer networks from oligo(ϵ-caprolactone)dimethacrylates (pages 1369–1381)

      Andreas Lendlein, Annette M. Schmidt, Michael Schroeter and Robert Langer

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20598

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      Polymer networks based on oligo(ϵ-caprolactone)dimethacrylates and showing a thermally induced shape-memory effect were synthesized and characterized. The networks were prepared by photocrosslinking with or without an initiator. The materials showed excellent shape-memory properties, which were quantified with thermocyclic tensile experiments.

    7. Cationic organoiron polyelectrolyte three-arm stars (pages 1382–1396)

      Alaa S. Abd-El-Aziz, Sarrah A. Carruthers, Erin K. Todd, Tarek H. Afifi and Jennilee M. A. Gavina

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20617

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      Star-shaped cationic organoiron polyelectrolytes were prepared with ether linkages, ester linkages, or both to probe the size dependence, solubility, viscosity, cyclic voltammetry, and thermal properties of the resultant molecules. In general, the addition of ester linkages to the ether star-shaped molecules reduced the solubility and thermal stability and increased the glass-transition temperature; increases in size had a similar effect.

    8. Newly synthesized polybenzoxazole derivative with an adjacent hydroxyphenyl ring for optical sensing (pages 1397–1403)

      Jin Koo Lee and Taek Seung Lee

      Version of Record online: 10 FEB 2005 | DOI: 10.1002/pola.20612

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      A polymer was studied that, acting as a fluorescent sensor toward metal cations, used intramolecular hydrogen bonding as a sensing module. Solutions of the polymer showed emission changes with the addition of metal ions. The effect was evident with exposure to magnesium or ferric ions.

    9. New poly(amidoamine)s containing disulfide linkages in their main chain (pages 1404–1416)

      Elisa Emilitri, Elisabetta Ranucci and Paolo Ferruti

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20599

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      Poly(amidoamine)s (PAAs) containing disulfide linkages in their backbones were obtained by the polyaddition of 2-methylpiperazine to N,N′-bis(acryloyl)cystamine or N,N′-bis(acryloyl)-(L)-cystine. The latter bisacrylamide led to an amphoteric PAA that contained two carboxyl groups per repeating unit and was, therefore, very soluble in water. The polymerization rates, determined with 1H NMR spectroscopy, were consistent with a pseudo-second-order mechanism. Degradation experiments carried out in the presence of 2-mercaptoethanol demonstrated that the disulfide group contained in the repeating units of both PAAs underwent reductive cleavage in the presence of thiols.

    10. Donor–acceptor copolymers for red- and near-infrared-emitting polymer light-emitting diodes (pages 1417–1431)

      Barry C. Thompson, Luis G. Madrigal, Mauricio R. Pinto, Tae-Sik Kang, Kirk S. Schanze and John R. Reynolds

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20578

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      A Heck polymerization has been utilized in the synthesis of vinylene linked alternating donor-acceptor copolymers based on pyridine or pyridopyrazine as the acceptor and 1,4-(2,5-dihexadecyloxy-phenylene) as the donor. In a systematic study, we illustrate that with the stronger pyridopyrazine acceptor, the enhanced done–acceptor interaction leads to a reduction in band gap from 2.1 eV to 1.8 eV for PPyrPV and PPyrPyrPV respectively. Photphysical studies are provided as support for the stronger donor–acceptor interaction. The polymers have been incorporated into LEDs, which emit in the NIR for the case of the PPyrPyrPV with an emission maximum at 800 nm.

    11. Atom transfer radical polymerization of styrenic ionic liquid monomers and carbon dioxide absorption of the polymerized ionic liquids (pages 1432–1443)

      Huadong Tang, Jianbin Tang, Shijie Ding, Maciej Radosz and Youqing Shen

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20600

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      Polyionic liquids are new polymeric materials with exceptional properties. Well-controlled poly(ionic liquids) were synthesized through the atom transfer radical polymerization of two styrenic ionic liquid monomers, 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate and 1-(4-vinylbenzyl)-3-butyl imidazolium hexafluorophosphate. The polymerized 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate (PVBIT) was amorphous and had excellent thermal stability, with a glass-transition temperature of 84 °C. The polymerized ionic liquids could absorb CO2 as ionic liquids: the 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate polymer absorbed 0.305% (w/w) CO2 at room temperature and 0.78 atm.

    12. Electrosyntheses of freestanding polyindole films in boron trifluoride diethyl etherate (pages 1444–1453)

      Jingkun Xu, Guangming Nie, Shusheng Zhang, Xuejun Han, Jian Hou and Shouzhi Pu

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20610

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      High quality free-standing polyindole (PIn) films, with good electrochemical behavior, high thermal stability, and conductivity of 10−1 S cm−1, were synthesized electrochemically by direct oxidation of indole in pure boron trifluoride diethyl etherate (BFEE). Structural studies showed that the polymerization of indole ring occurred at 2,3 position. As formed PIn films can be partly dissolved in acetone, a cetonitrile, tetrahydrofuran, etc. Fluorescent spectral studies indicated that PIn is a good blue-light emitter. To the best of our knowledge, this is the first report on the fluorescence of PIn.

    13. Synthesis of regioregular poly(3-octylthiophene)s via Suzuki polycondensation and end-group analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (pages 1454–1462)

      M. Jayakannan, X. Lou, Joost L. J. van Dongen and René A. J. Janssen

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20618

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      Regioregular poly(3-octylthiophene)s were synthesized by palladium catalyzed Suzuki polycondensation and the role of the palladium catalyst and reaction conditions was investigated. MALDI-TOF mass spectrometry was used to analyze end groups and allowed to determine mechanistic aspects of the Suzuki polycondensation. Utilizing Pd(dppf)Cl2 as a catalyst only hydrogen terminated H-Tn-H chains could be detected, providing a very clean synthetic route to highly regioregular polythiophenes.

    14. Synthesis and characterization of novel biodegradable unsaturated poly(ester amide)s (pages 1463–1477)

      Kai Guo, C. C. Chu, E. Chkhaidze and R. Katsarava

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20463

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      A new family of novel biodegradable unsaturated poly(ester-amide)s (UPEAs) were synthesized by solution polycondensation. The molecular weights (Mn and Mw of UPEAs measured by GPC ranged from 10∼30 kg/mol with a rather narrow molecular weight distribution of 1.40. The chemical structures of these novel biodegradable UPEAs were confirmed by IR, NMR, and elemental analysis. The most unique aspect of these UPEAs is the built-in C[DOUBLE BOND]C double bonds in the UPEA backbones. As a result, these UPEAs will have the potent functionality of C[DOUBLE BOND]C bonds, such as photochemical reactivity or capability to react with or be modified by other bioactive or other environmental sensitive compounds. This capability could extend the PEA applications to many different fields, such as biomedical and environmental areas.

    15. Synthesis of poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) block copolymers by CuCl/2,2′-bipyridine-catalyzed living radical block copolymerization initiated from α,ω-di(iodo)poly(vinyl chloride) prepared by single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization (pages 1478–1486)

      Virgil Percec, Tamaz Guliashvili, Anatoliy V. Popov and Ernesto Ramirez-Castillo

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20604

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      Poly(methyl methacrylate)-b-poly(vinyl chloride)-b-poly(methyl methacrylate) (PMMA-b-PVC-b-PMMA) block copolymers were synthesized by the CuCl/2,2′-bipyridine (bpy)-catalyzed living radical polymerization of methyl methacrylate (MMA) initiated from the chain ends of α,ω-di(iodo)poly(vinyl chloride) in diphenyl ether at 90 °C.

    16. Concentration effects in the cationic ring-opening polymerization of 2-ethyl-2-oxazoline in N,N-dimethylacetamide (pages 1487–1497)

      Richard Hoogenboom, Renzo M. Paulus, Martin W. M. Fijten and Ulrich S. Schubert

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20603

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      The monomer concentration for the cationic ring-opening polymerization of 2-ethyl-2-oxazoline in N,N-dimethylacetamide was optimized utilizing high-throughput experimentation methods. The underlying mechanisms responsible for the optimal concentration range were further investigated by detailed 1H-NMR spectroscopic investigations. As a final point, the most favorable concentration was applied for the synthesis of higher molecular weight (> 10,000 dalton) poly(2-ethyl-2-oxazoline)s. The graphical abstract depicts selected kinetic results and GPC traces from the polymerizations at both 1 and 8 M monomer concentration.

    17. Block and random copolymers as surfactants for dispersion polymerization. I. Synthesis via atom transfer radical polymerization and ring-opening polymerization (pages 1498–1510)

      Wojciech Jakubowski, Jean-François Lutz, Stanislaw Slomkowski and Krzysztof Matyjaszewski

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20629

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      Atom transfer radical polymerization and anionic ring-opening polymerization were combined to synthesize poly(ϵ-caprolactone-co-octadecyl methacrylate-co-dimethylaminoethyl methacrylate) copolymers possessing either a triblock or random block structure. Various synthetic pathways (sequential or simultaneous approaches) were investigated for the synthesis of both copolymers. The synthesized copolymers were targeted as surfactants that could stabilize poly(L-lactide) microspheres in organic and aqueous media.

    18. Synthesis and optical and electrochemical properties of thermotropic, liquid-crystalline, semirigid copolyesters based on 2,5-diphenyl-1,3,4-thiadiazole units (pages 1511–1525)

      Moriyuki Sato, Yuji Tada, Shinji Nakashima, Ken-ichi Ishikura, Makoto Handa and Kuninobu Kasuga

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20606

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      New thermotropic liquid-crystalline copolyesters containing three disubstituted (4,4′-, 3,4′-, and 3,3′-) 2,5-diphenyl-1,3,4-thiadiazole (DPTD) units were synthesized, and their optical and electrochemical properties were examined. The copolyesters displayed ultraviolet–visible absorptions and photoluminescent lights with blue emission in the solid states. The mesomorphic tendency and the peak maxima of absorption and emission spectra decreased and shifted to lower wave lengths in the order of 4,4′- and 3,4′-DPTD copolymers > 4,4′- and 3,3′-DPTD copolymers > 3,4′- and 3,3′-DPTD copolymers. The copolymers had better charge-injection balance than PPV-based polyoxadiazole.

    19. Solid-state polymerization of 2,3,6,7,10,11-hexa(methacrylate) triphenylene (pages 1526–1534)

      Xiang Yu, Yangbin Chen, Caiyuan Pan, Yan Di and Junying Zhang

      Version of Record online: 15 FEB 2005 | DOI: 10.1002/pola.20635

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      The solid-state polymerization of a new monomer, 2,3,6,7,10,11-hexa(methacrylate) triphenylene (HMTP) is crystal form, was carried out under UV irradiation, and polymer crystals was formed. The FT-IR spectroscopy was used to follow the photopolymerization of HMTP in solid state, which showed the first-order reaction with rate constant of 6.12 × 10−3 min−1. In comparison with the polarizing optical microscope and X-ray diffraction images of its precursor, the product obtained remained the monomer crystal lattice, and the polymerization is governed by packing structure of monomer molecules.

    20. α-Cyanobenzyl dithioester reversible addition–fragmentation chain-transfer agents for controlled radical polymerizations (pages 1535–1543)

      Chunzhao Li and Brian C. Benicewicz

      Version of Record online: 14 FEB 2005 | DOI: 10.1002/pola.20658

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      Dithioesters containing α-cyanobenzyl groups were effective chain-transfer agents for the controlled radical (via reversible addition–fragmentation chain transfer) polymerization of important monomers such as styrenics, acrylates, and methyl methacrylate. These compounds contained secondary R groups and produced polymers and block copolymers with predictable molecular weights and narrow polydispersity indices.

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