Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 4

15 February 2005

Volume 43, Issue 4

Pages 693–916

  1. Highlight

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    3. Articles
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    5. Erratum
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      Challenge of synthetic cellulose (pages 693–710)

      Shiro Kobayashi

      Article first published online: 28 DEC 2004 | DOI: 10.1002/pola.20662

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      Synthetic cellulose was realized for the first time through an enzymatic polycondensation of β-D-cellobiosyl fluoride catalyzed by cellulose. The reaction opened a door to enzymatic polymerization, enabling the synthesis of natural and unnatural polysaccharides, and led to a concept of a transition-state analogue substrate monomer for the synthesis of various polymers.

  2. Articles

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    1. An experimental and computational evaluation of ethylene/styrene copolymerization with a homogeneous single-site titanium(IV)-constrained geometry catalyst (pages 711–725)

      S. Martínez, M. T. Exposito, J. Ramos, V. Cruz, M. C. Martínez, M. López, A. Muñoz-Escalona and J. Martínez-Salazar

      Article first published online: 28 DEC 2004 | DOI: 10.1002/pola.20456

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      Styrene was copolymerized with ethylene using the geometry constrained Me2Si(Me4Cp)(N-tert-butyl)TiCl2 Dow catalyst activated with methylaluminoxane under well-controlled experimental reaction conditions. We discuss the experimental findings within the framework of a computational analysis of ethylene/styrene copolymerization performed through hybrid density functional theory (B3LYP). In general, there was good agreement between the experimental and theoretical results. Our findings point to the suitability of combining experimental and theoretical data for clarifying the copolymerization mechanisms that take place in α-olefin–organometallic systems.

    2. Electrosteric stability of styrene/acrylic acid copolymer latices under emulsion polymerization reaction conditions (pages 726–732)

      Xaviera E. E. Reynhout, Mark Beckers, Jan Meuldijk and Bart A. H. Drinkenburg

      Article first published online: 28 DEC 2004 | DOI: 10.1002/pola.20547

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      Acrylic acid is used in many emulsion polymerization formulations to improve the colloidal stability of the latex product. The contribution of electrostatic and steric repulsion forces to the colloidal stability of swollen polystyrene and styrene/acrylic acid copolymer latexes was investigated at different pH values, electrolyte concentrations, and temperatures. Transmission electron microscopy (TEM) was combined with dynamic light scattering (DLS) to reveal and visualize what really happens at particle level when colloidal stability is lost. The incorporation of acrylic acid did not improve the colloidal stability of latexes under reaction conditions, i.e., high temperature, low pH, and monomer swollen particles. For the produced copolymer latexes electrosteric stability was found to depend significantly stronger on the pH as on temperature.

    3. Synthesis of a novel liquid crystal rod–coil star block copolymer consisting of poly(methyl methacrylate) and poly{2,5-bis[(4-methoxy-phenyl)oxycarbonyl] styrene} via atom transfer radical polymerization (pages 733–741)

      Xingzhu Wang, Hailiang Zhang, Mao Shi, Xiayu Wang and Qifeng Zhou

      Article first published online: 4 JAN 2005 | DOI: 10.1002/pola.20540

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      A bromine capped star-shaped poly(methyl methacrylate) (S-PMMA-Br) was synthesized with CuBr/sparteine/PT-Br as a catalyst and initiator to polymerize methyl methacrylate (MMA) according to atom transfer radical polymerization (ATRP). Then, with S-PMMA-Br as a macroinitiator, a series of new liquid crystal rod–coil star block copolymers with different molecular weights and low polydisperisity were obtained by this method. The block architecture {coil-conformation of the MMA segment and rigid-rod conformation of 2,5-bis[(4-methoxyphenyl)oxycarbonyl] styrene segment} of the four-armed rod–coil star block copolymers were characterized by 1H NMR. The liquid-crystalline behavior of these copolymers was studied by differential scanning calorimetry and polarized optical microscopy. We found that the liquid-crystalline behavior depends on the molecular weight of the rigid segment; only the four-armed rod–coil star block copolymers with each arm's Mn,GPC of the rigid block beyond 0.91 × 104 g/mol could form liquid-crystalline phases above the glass-transition temperature of the rigid block.

    4. Versatile preparation of poly(1,4-phenylenevinylene-co-1,4-phenylene-1,2-ethanediyl) by CVD polymerization of p-(methoxymethyl)benzyl chloride (pages 742–751)

      Ngo Trinh Tung, Young-Jun Yu, Kyungkon Kim, Sung-Hoon Joo, Yongsup Park and Jung-Il Jin

      Article first published online: 4 JAN 2005 | DOI: 10.1002/pola.20537

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      It was demonstrated that a series of copolymers consisting of 1,4-phenylenevinylene (PV) and 1,4-phenylene-1,2-ethanediyl (PE) units could be prepared from a single monomer, p-(methoxymethyl)benzyl chloride via the chemical vapor deposition polymerization (CVDP) method. The compositions of the copolymers could be varied by simply altering the monomer activation temperature. The higher the temperature, the lower the content of the PV unit became.

    5. Atom transfer radical polymerization of 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose in solution (pages 752–762)

      Jian-Qiang Meng, Fu-Sheng Du, Ya-Shu Liu and Zi-Chen Li

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20568

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      A detailed exploration of the atom transfer radical polymerization (ATRP) of a sugar-carrying monomer, 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose (MAIPGal) was performed. The best control of polymerization can be achieved by initiation with 2-EBiB at room temperature with PMDETA as the ligand. Well-defined glycopolymer or block copolymers containing a glycopolymer segment were obtained after removal of the protecting groups.

    6. Synthesis, isolation, and characterization of polytitanasiloxanes and zirconasiloxanes by the hydrolytic cocondensation of tetraethoxysilane and titanium or zirconium tetraisopropoxide (pages 763–772)

      Takahiro Gunji, Masanari Yokogawa, Masahiro Hongo and Yoshimoto Abe

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20546

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      The hydrolytic cocondensation of tetraethoxysilane (TEOS) and tetraisopropoxytitanium or tetraisopropoxyzirconium (process A) and the condensation of partially hydrolyzed TEOS with the metal alkoxides (process B), followed by an in situ reaction with acetylacetone, provided polymetallasiloxanes stable against self-condensation. This allowed their isolation and the investigation of their structures from the results of elemental and spectral analyses and of their crystallization behavior from a thermal treatment. The formation of random and block Si[BOND]O[BOND]M backbone linkages of the polymetallasiloxanes appeared to result from processes A and B, respectively.

    7. Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride initiated with methylene iodide and catalyzed by sodium dithionite (pages 773–778)

      Virgil Percec, Anatoliy V. Popov, Ernesto Ramirez-Castillo and Jorge F. J. Coelho

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20543

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      Single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) initiated with methylene iodide (CH2I2) and catalyzed by sodium dithionite (Na2S2O4) in water at 35 °C produces a telechelic poly(vinyl chloride) with two different active chain ends: ICH2(CH2CHCl)n-1CH2CHClI. The reactivity and initiator efficiency of CH2I2 in SET–DTLRP of VC was lower than that of iodoform. A possible mechanism for the CH2I2-initiated SET–DTLRP of VC is suggested.

    8. Phase transfer catalyzed single electron transfer–degenerative chain transfer mediated living radical polymerization (PTC-SET–DTLRP) of vinyl chloride catalyzed by sodium dithionite and initiated with iodoform in water at 43 °C (pages 779–788)

      Virgil Percec, Anatoliy V. Popov, Ernesto Ramirez-Castillo, Jorge F. J. Coelho and Luis A. Hinojosa-Falcon

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20544

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      A catalytic amount of the phase-transfer catalyst (PTC) cetyltrimethylammonium bromide (nC16H33(CH3)3N+Br, CetMe3NBr) accelerates the fast stage of sodium dithionite (Na2S2O4) catalyzed single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) initiated with iodoform (CHI3) in water at 43 °C.

    9. Preparation of ultrahigh-molecular-weight syndiotactic poly(vinyl pivalate) monodisperse microspheres by low-temperature suspension polymerization of vinyl pivalate (pages 789–800)

      Won Seok Lyoo, Jin Woo Kwak, Jeong Hyun Yeum, Byung Chul Ji, Chul Joo Lee and Seok Kyun Noh

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20538

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      The particle size distributions of poly(vinyl pivalate) (PVPi) produced from low-temperature suspension polymerization of vinyl pivalate (VPi) using 2,2′azobis(4-methoxy-2,4-dimethylvaleronitrile) (AMDMVN) as an initiator have been studied. By controlling vaious synthesis parameters, near-monodisperse PVPi microspheres from 100 μm to 400 μm were obtained, which are expected to be a precursor of near-monodisperse syndiotactic poly(vinyl alcohol) (PVA) microspheres for biomedical embolic applications. The mean particle diameter follows the relationship: the volume average diameter, DvadY0.26[VPi]0.52[AMDMVN]−0.25[PVA]0.40T−8.35Rpm−0.67, where Y, [VPi], [AMDMVN], [PVA], T, and Rpm are the fractional conversion, concentrations of VPi, AMDMVN, and suspending agent, polymerization temperature, and agitation speed during polymerization of VPi, respectively. Ultrahigh molecular weight PVPi and PVA (number-average degrees of polymerization of PVPi (25,000–32,000) and PVA (14,000–17,500), of high syndiotactic diad content (63%), and of high ultimate conversion of VPi into PVPi (85–95%) were obtained by suspension polymerization at 10 °C followed by saponification.

    10. Development of an improved synthetic route to an AB phenylquinoxaline monomer (pages 801–814)

      Jong-Beom Baek and Frank W. Harris

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20528

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      An efficient synthetic route to a self-polymerizable phenylquinoxaline monomer mixture, 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline and 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline, was developed. Thus, the intermediate, 4-hydroxybenzil, was synthesized in two steps starting directly from phenol with phenylacetyl chloride via Fries rearrangement to afford 4-phenylacetylphenol. The other intermediate, 4-fluoro-1,2-phenylenediamine, was also less costly synthesized starting from 2,4-difluoronitrobenzene instead of expensive 2,5-difluoronitrobenzene with ammonium hydroxide followed by reduction giving an excellent yield.

    11. Synthesis and characterization of single-wall-carbon-nanotube-doped emeraldine salt and base polyaniline nanocomposites (pages 815–822)

      Gustavo M. Do Nascimento, Paola Corio, Richard W. Novickis, Marcia L. A. Temperini and Mildred S. Dresselhaus

      Article first published online: 5 JAN 2005 | DOI: 10.1002/pola.20551

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      Nanocomposites of polyaniline (PANI) in conducting [PANI emeraldine salt (PANI-ES)] and insulating [PANI emeraldine base (PANI-EB)] forms and single-wall carbon nanotubes were investigated. A very different behavior between the metallic and semiconducting carbon nanotubes toward the chemical interaction with PANI was found. An intense charge-transfer process occurred between the PANI emeraldine salt and metallic single-wall carbon nanotubes, and the electronic structure was significantly perturbed.

    12. Light-emitting copolymers based on fluorene and selenophene—Comparative studies with its sulfur analogue: Poly(fluorene-co-thiophene) (pages 823–836)

      Renqiang Yang, Renyu Tian, Qiong Hou, Yong Zhang, Yongfang Li, Wei Yang, Chi Zhang and Yong Cao

      Article first published online: 6 JAN 2005 | DOI: 10.1002/pola.20562

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      A series of fluorene-based copolymers with various ratios of selenopene (SeH) was synthesized by a palladium-catalyzed Suzuki coupling reaction. The efficient energy transfer from fluorene segments to narrow band-gap SeH sites was observed. In comparison with the emission spectra of very well studied copolymer poly(fluorene-co-thiophene), the SeH-containing polymers show significantly redshifted PL and EL emissions. The device fabricated with PFO-SeH15 as the emissive layer exhibited external quantum efficiency (0.51%) at luminance of 1570 cd/m2 with emission peak at 490 nm.

    13. Synthesis, characterization, and degradation of silicon(IV) phthalocyanines conjugated axially with poly(sebacic anhydride) (pages 837–843)

      Priscilla P. S. Lee, To Ngai, Cheng Yang, Chi Wu and Dennis K. P. Ng

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20561

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      The preparation, spectroscopic properties together with the nanoparticle formation and degradation of a novel silicone (IV) phthalocyanine with two axial poly(sebacic anhydride) chains are described.

    14. Semibatch emulsion polymerization of methyl methacrylate using different polyurethane particles (pages 844–858)

      Urška Šebenik and Matjaz̆ Krajnc

      Article first published online: 7 JAN 2005 | DOI: 10.1002/pola.20559

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      Aqueous acrylic-polyurethane (AC–PU) hybrid emulsions were prepared by semibatch emulsion polymerization of methyl methacrylate (MMA) in the presence of four polyurethane (PU) dispersions. We studied the effect of the use of different PU seed particles on the rate of polymerization, the particle size and distribution, the number of particles, and the average number of radicals per particle.

    15. Polyfluorene containing diphenylquinoline pendants and their applications in organic light emitting diodes (pages 859–869)

      Huei-Jen Su, Fang-Iy Wu, Ching-Fong Shu, Yung-Liang Tung, Yun Chi and Gene-Hsiang Lee

      Article first published online: 7 JAN 2005 | DOI: 10.1002/pola.20569

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      A light emitting diode (LED) device prepared with PF-Q as the emitting layer exhibits a stable blue emission with a maximum brightness of 1121 cd/m2 at 12 V and a maximum external quantum efficiency of 0.80% at 250 cd/m2. Moreover, with PF-Q as the host material and doping it with 2.4 wt % of a red-emitting osmium complex, we realized a red electroluminescent device with a maximum brightness of 10457 cd/m2 and CIE coordinates of (0.66, 0.34).

    16. Controlled anionic synthesis of star-shaped polystyrene by the incremental addition of divinylbenzene (pages 870–878)

      Hyung-Jae Lee, Kwanyoung Lee and Namsun Choi

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20572

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      The incremental addition of divinylbenzene (DVB) to polystyryllithium (PSLi) effectively synthesized star-shaped polystyrene, minimizing uncoupled polystyrene and reproducibly controlling the arm number of star polystyrene without the formation of gel content.

    17. New polyphenylene-g-polystyrene and polyphenylene-g-polystyrene/poly(ε-caprolactone) copolymers by combined controlled polymerization and cross-coupling processes (pages 879–896)

      Seda Yurteri, Ioan Cianga, A. Levent Demirel and Yusuf Yagci

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20565

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      Polystyrene (PSt)-based macromonomers, synthesized by atom transfer radical polymerization and possessing at one end a 2,5-dibromophenylene or 3,5-dibromophenylene moiety, were used in combination with 2,5-dihexylbenzene-1,4-diboronic acid for Suzuki coupling or in Yamamoto polymerization. The same macromonomers were used in Yamamoto copolycondensation reactions, in combination with a poly(ε-caprolactone) (PCL) macromonomer, and this resulted in polyphenylenes (PPs) with PSt/PCL side chains. The new polymers were characterized with spectral methods. The thermal behaviors of the macromonomers and final PPs were investigated with differential scanning calorimetry and compared. The morphology of PPs containing PSt and PCL blocks was characterized with atomic force microscopy, and a microphase-separated layered morphology was observed.

    18. Nuclear magnetic resonance monitoring of chain-end functionality in the atom transfer radical polymerization of styrene (pages 897–910)

      Jean-François Lutz and Krzysztof Matyjaszewski

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20548

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      The bromine chain-end functionality of polystyrene prepared using atom transfer radical polymerization was monitored by 600 MHz proton NMR. During polymerization, a decrease in functionality versus conversion was observed. The loss of functionality was especially significant at very high conversions (>90%). The loss of chain-end functionality was partly due to bimolecular terminations but mainly due to β-H elimination reactions, induced by the copper (II) deactivator. Understanding these side reactions helped to select proper conditions to reduce the contribution of the elimination process and to prepare well-defined polystyrene (Mn ∼ 10000 g mol−1; Mw/Mn ∼ 1.1) with high functionality (f = 92%).

  3. Rapid Communication

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    5. Erratum
    1. Copolymerization of ethylene and N-(vinylphenyl)carbazole with titanium and zirconium catalysts (pages 911–915)

      Naofumi Naga, Akinori Toyota and Kenji Ogino

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20597

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      Copolymerization of ethylene and N-(vinylphenyl)carbazole (VPC) was investigated with dimethylsilylene(tetramethylcyclopentadienyl)(N-tert-butyl)titanium dichloride (1) and isopropylidenebis(indenyl)zirconium dichloride (2) catalysts. The corresponding copolymers were obtained in the copolymerization, and the copolymerization behavior and structure of the resulting copolymer were studied.

  4. Erratum

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      Copolymerization of carbon dioxide and epoxide (page 916)

      Hiroshi Sugimoto and Shohei Inoue

      Article first published online: 10 JAN 2005 | DOI: 10.1002/pola.20716

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