Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 9

1 May 2005

Volume 43, Issue 9

Pages 1747–1984

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Evaluation of initiator systems for controlled and sequentially curable free-radical/cationic hybrid photopolymerizations (pages 1747–1756)

      Joe D. Oxman, Dwight W. Jacobs, Matthew C. Trom, Vishal Sipani, Beth Ficek and Alec B. Scranton

      Version of Record online: 10 MAR 2005 | DOI: 10.1002/pola.20641

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      Free-radical/cationic hybrid photopolymerizations of acrylates and epoxides were initiated using a three-component initiator system comprised of camphorquinone as the photosensitizer, an amine as the electron donor, and a diaryliodonium salt. To be effective, it was found that the electron donor must have an oxidation potential of less than 1.34 V relative to SCE and a pKb higher than 8. Experiments performed using a combination of electron donors revealed that the onset of the hybrid system's cationic polymerization can be advanced or delayed by controlling the concentration and composition of the electron donor(s). These studies demonstrate that a single three-component initiator system can be used to initiate and chemically control the sequential curing properties of a free-radical/cationic hybrid photopolymerization and is a viable alternative to separate photoinitiators for each type of polymerization.

    2. Nonstoichiometric polycondensation of 4-acetoxybenzoic acid in the presence of monoacetate (pages 1757–1766)

      Shin-ichiro Kohama, Kunio Kimura and Yuhiko Yamashita

      Version of Record online: 11 MAR 2005 | DOI: 10.1002/pola.20651

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      Preparation of poly(4-oxybenzoyl) (POB) was examined by nonstoichiometric polycondensation of 4-acetoxybenzoic acid in the presence of three kinds of aromatic monoacetates: 4-hexyloxyphenyl acetate, 4-decyloxyphenyl acetate, and 4-octadecyloxyphenyl acetate. Polymerizations were carried out in liquid paraffin at 320 °C. High molecular weight POB was obtained as crystals when the molar ratio of monoacetates in feed was less than 80 mol %. Polymer was synthesized even under nonstoichiometric conditions by means of the crystallization of oligomers and the following solid-state polymerization in the crystals.

    3. Syntheses and characterizations of aniline/butylthioaniline copolymers: Comparisons of copolymers prepared by the new concurrent reduction and substitution route and the conventional oxidative copolymerization method (pages 1767–1777)

      Chien-Chung Han, Ku-Feng Yang, Shih-Ping Hong, Arumugam Balasubramanian and Yi-Te Lee

      Version of Record online: 14 MAR 2005 | DOI: 10.1002/pola.20660

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      New highly solution-processable aniline/butylthioaniline copolymers were prepared via oxidative copolymerization (OCP) and by concurrent reduction and substitution (CRS). Butylthio-substituted polyaniline obtained via the CRS route (Pan-SBu), being in line with the expected property changes after the addition of an electron-donating substituent to an aromatic ring, displayed a lowered redox potential (E0) and a redshifted maximum wavelength (λmax; ultraviolet–visible) in comparison with its parent unsubstituted polyaniline (Pan). However, copolymers CP1–CP4 (obtained via the OCP method) displayed opposite behaviors, showing higher E0 values and blueshifts in λmax than the unsubstituted Pan. The results suggested that CP1–CP4 had shorter conjugation lengths than the unsubstituted Pan, possibly because of their chain conjugation defects (e.g., 1,3-ring linkage structures), as evidenced by IR studies.

    4. Homoleptic lanthanide guanidinate complexes: The effective initiators for the polymerization of trimethylene carbonate and its copolymerization with ε-caprolactone (pages 1778–1786)

      Liying Zhou, Hongmei Sun, Jinglei Chen, Yingming Yao and Qi Shen

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20644

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      The ring-opening polymerization of trimethylene carbonate (TMC) using homoleptic lanthanide guanidinate complexes [RNC(NRmath image)NR]3Ln as single component initiators has been fully investigated. The polymerization was proposed to occur via acyl-oxygen bond cleavage.

    5. Synthesis and characterization of poly(DTC-b-PEG-b-DTC) triblock and poly(TMC-b-DTC-b-PEG-b-DTC-b-TMC) pentablock copolymers and kinetics of the polymerization (pages 1787–1796)

      Jun Ling, Wei Chen and Zhiquan Shen

      Version of Record online: 16 MAR 2005 | DOI: 10.1002/pola.20648

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      Dihydroxyl capped biodegradable triblock and pentablock copolymers have been synthesized. The Monte Carlo method has been developed to estimate the chain propagation constant and exchange reaction constant.

    6. Investigation of the microstructure of polypropylene prepared with ansa and fluxional metallocene catalysts with an extended Coleman–Fox model (pages 1797–1810)

      Márcio Nele, José Carlos Pinto, Muqtar Mohammed and Scott Collins

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20657

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      The combined effects of temperature and monomer concentration on the microstructure of polypropylene prepared with two-state ansa and fluxional metallocene catalysts were modeled using a modified Colleman–Fox approach. Comparison with experimental data, for the PP prepared with Me2Si(Ind)(Flu)ZrCl2/MAO, showed that the model was able to predict very well the observed polymer microstructure at the pentad level.

    7. Synthesis and characterization of novel dendritic (arborescent, hyperbranched) polyisobutylene–polystyrene block copolymers (pages 1811–1826)

      Judit E. Puskas, Yongmoon Kwon, Prince Antony and Anil K. Bhowmick

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20638

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      The synthesis of novel arborescent (arb; randomly branched, “tree-like,” and often called “hyperbranched”) block copolymers comprised of rubbery polyisobutylene (PIB) and glassy polystyrene (PSt) blocks (arb-PIB-b-PSt) is described. arb-PIB-b-PSt with 11.7–33.8 wt % PSt and Mn = 468,800–652,900 g/mol displayed thermoplastic elastomeric properties with 3.6–8.7 MPa tensile strength and 950–1830% elongation. arb-PIB-b-PSt swelled five times as much as a linear block copolymer, and XPS showed that the surface of the blocks is covered with a 10 nm thin PIB layer.

    8. Transition structures and reaction barriers in the styrene–acrylonitrile copolymerization system according to quantum mechanical calculations (pages 1827–1844)

      Andrzej Kaim and Elżbieta Megiel

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20652

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      The geometries and electronic properties of substrates, transition structures (TS), and product propagating radicals in elementary propagation reactions according to the terminal kinetic model of copolymerization were studied for the styrene–acrylonitrile monomer system by use of quantum mechanical calculations (DFT/B3-LYP/6–311+G(3df,2p)//DFT/B3-LYP/6–31G(d)). For modeled homopolymerization of acrylonitrile, CH3A•+A, ΔHact = 36.5 kJ/mol and ΔHr = −57.1 kJ/mol were evaluated.

    9. Fluorene-based alternating polymers containing electron-withdrawing bithiazole units: Preparation and device applications (pages 1845–1857)

      Jaemin Lee, Byung-Jun Jung, Sang Kyu Lee, Jeong-Ik Lee, Hoon-Je Cho and Hong-Ku Shim

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20659

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      Two novel alternating polymers based on fluorene and electron-withdrawing bithiazole, poly[(4,4′-dihexyl-2,2′-bithiazole-5,5′-diyl)-alt-(9,9-dioctylfluorene-2,7-diyl)] (PHBTzF) and poly[(5,5′-bis(2″-thienyl)-4,4′-dihexyl-2,2′-bithiazole-5″,5″-diyl)-alt-(9,9-dioctylfluorene-2,7-diyl)] (PTHBTzTF), were synthesized by Suzuki polymerization. The physical and optical properties of the polymers were carefully characterized. The addition of bithiazole to the polymers' main chain not only reduced the lowest unoccupied molecular orbital energy levels of the polymers but also improved their n-doping stability. Polymeric light-emitting-diode devices and organic solar-cell devices with the polymers as active layers showed the potential of these kinds of materials for use in organic electronic devices.

    10. Synthesis of ethylene/propylene elastomers containing a terminal reactive group: The combination of metallocene catalysis and control chain transfer reaction (pages 1858–1872)

      U. Kandil and T. C. Chung

      Version of Record online: 15 MAR 2005 | DOI: 10.1002/pola.20672

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      New ethylene/propylene (EP) copolymers containing a terminal reactive group, such as ϕ-CH3 and OH, have been prepared by a combination of selective metallocene catalyst and a mixture of hydrogen and styrene derivatives carrying a CH3 (p-MS) or a silane-protected OH (St-OSi).

    11. Nitroxide-mediated homo- and block copolymerization of styrene and multifunctional acryl- and methacryl derivatives (pages 1873–1882)

      Meizhen Yin, Tilo Krause, Martin Messerschmidt, Wolf D. Habicher and Brigitte Voit

      Version of Record online: 16 MAR 2005 | DOI: 10.1002/pola.20667

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      The block copolymerization of multifunctional acryl- and methacryl derivatives using a polystyrene macroinitiator, made by nitroxide-mediated radical polymerization initiated by 2-hydroxymethyl-2-[(2-methyl-1-phenyl-propyl)-(1-phenyl-ethoxy)-amino]-propane-1,3-diol (I5), led to novel amphiphilic block copolymers with narrow molecular weight distribution.

    12. Synthesis and characterization of ultraviolet-curable hyperbranched poly(siloxysilane)s (pages 1883–1894)

      Qing-Fa Si, Xin Wang, Xiao-Dong Fan and Sheng-Jie Wang

      Version of Record online: 16 MAR 2005 | DOI: 10.1002/pola.20675

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      UV-curable hyperbranched poly(siloxysilane)s containing vinyl, allyl, an epoxy end groups were synthesized via polyhdyrosilylation of AB2 type monomers. The curing behaviors of hyperbranched polymers in different atmospheres and different photoaccelerators were investigated. The results showed that the photoactivity of the hyperbranched polymers with allyl and epoxy end groups initiated by the same photoinitiator was higher than that of the hyperbranched polymer with vinyl end groups.

    13. New poly(oxyethylene) derivatives and their oligo analogues from Diels–Alder reactions of 5-[methoxypoly(oxyethylene)]-(3E)-1, 3-pentadiene and 5-methoxyethoxy-(3E)-1,3-pentadiene (pages 1895–1902)

      Timothy E. Hopkins, Moa Park, Almary Chacon and Reza Sedaghat-Herati

      Version of Record online: 16 MAR 2005 | DOI: 10.1002/pola.20656

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      This article describes the syntheses and characterizations of new poly(oxyethylene) derivatives and their oligo analogues from the Diels–Alder reactions of 5-[methoxypoly(oxyethylene)]-(3E)-1,3-pentadiene (1a) and 5-methoxyethoxy-(3E)-1,3-pentadiene (1b).

    14. Main chain thermotropic liquid crystalline polyurethanes containing biphenyl mesogens based on novel AB-type self-polycondensation route: FT-IR and XRD studies (pages 1903–1912)

      T. Ranganathan, E. Bhoje Gowd, C. Ramesh and Anil Kumar

      Version of Record online: 22 MAR 2005 | DOI: 10.1002/pola.20668

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      The detailed mesophasic characterization of main chain liquid crystalline polyurethanes containing biphenyl mesogen, which were synthesized by the novel AB-type self-polycondensation approach, was carried out by using differential scanning calorimetry (DSC), optical polarized microscopy (OPM), variable temperature X-ray diffraction (XRD), and fourier transform infrared (FT-IR) spectroscopic studies.

    15. Less toxic acetylacetonates as initiators of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate ring opening polymerization (pages 1913–1922)

      Piotr Dobrzynski, Malgorzata Pastusiak and Maciej Bero

      Version of Record online: 22 MAR 2005 | DOI: 10.1002/pola.20670

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      This paper presents the results of TMC and DMC polymerization with the use of acetylacetonates of low-toxic metals: iron, zinc, and zirconium. Zinc (II) acetylacetonate proves to be a very good initiator of homopolymerization. A strong influence of thermal degradation on the course of the reaction was observed, particularly at 160 °C with the use of Fe(acac)3 as the initiator. DMC polymerization proceeds much more slowly when initiated by iron and zinc acetylacetonates. A high conversion of the monomer is obtained in this case as well.

    16. One-pot synthesis of linear and branched poly(amide aspartimide)s with good solubility in organic solvents (pages 1923–1929)

      Chuan-Shao Wu, Shr-Hau Tsai and Ying-Ling Liu

      Version of Record online: 22 MAR 2005 | DOI: 10.1002/pola.20663

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      Linear and branched poly(amide-aspartimide)s were prepared from reacting 4,4′-diaminodiphenylmethane (DDM) with 4-maleimidobenzoic acid (MBA) and 5-maleimidoisophthalic acid (MIPA), respectively. The synthesis was performed through a one-pot operation by means of the Michael addition reaction between amine/maleimide groups and the dehydration condensation reaction beween amine/carboxylic acid groups. The polymers obtained exhibited fairly good solubility in aprotic polar solvents at room temperature, and in pyridine, tetrahydrofuran, acetone, and chloroform upon heating. High glass-transition temperatures at 225 °C and above and thermal stability above 360 °C were found with the polymers.

    17. Growth of polystyrene films via gas-phase polymerization with [Pd(CH3CN)4][BF4]2 thin film catalyst (pages 1930–1934)

      Kimberly S. Wain, Ayusman Sen and Seong Han Kim

      Version of Record online: 22 MAR 2005 | DOI: 10.1002/pola.20671

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      The heterogeneous catalytic polymerization of styrene vapor with a tetrakis(acetonitrile)palladium(II) tetrafluoroborate, [Pd(CH3CN)4]-[BF4]2, thin film has been demonstrated. The catalyst is deposited by nebulization of dilute solutions onto a quartz crystal microbalance (QCM) and then exposed to styrene vapor in controlled environments. The use of QCM allows in-situ monitoring of catalyst deposition and polymer growth kinetics. The polymerization process appears to involve the entire catalyst film rather than polymerization only at the catalyst film surface. The styrene vapor polymerization occurs rapidly after a short induction time needed for monomer dissolution and catalyst activation. The narrow molecular weight distribution of the produced polymer suggests that the deposited film acts as a single-site catalyst.

    18. Catalytic effect of dimethyl sulfoxide in the Cu(0)/tris(2-dimethylaminoethyl)amine-catalyzed living radical polymerization of methyl methacrylate at 0–90 °C initiated with CH3CHClI as a model compound for α,ω-di(iodo)poly(vinyl chloride) chain ends (pages 1935–1947)

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

      Version of Record online: 22 MAR 2005 | DOI: 10.1002/pola.20614

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      CH3CHClI initiates the Cu(0)/tris(2-dimethylaminoethyl)amine (Me6-TREN)-catalyzed living radical polymerization (LRP) of methyl methacrylate (MMA) in dimethyl sulfoxide (DMSO) at 0–90 °C. Poly(methyl methacrylate)s (PMMAs) obtained by this LRP at different temperatures have different tactiticities and glass-transition temperatures. This polymerization exhibits an external first order of reaction in DMSO and therefore provides the first example of a solvent that displays catalytic activity. Other catalysts, solvents, and ligands have also been tested in this metal-catalyzed LRP of MMA.

    19. Ultrafast synthesis of poly(methyl acrylate) and poly(methyl acrylate)-b-poly(vinyl chloride)-b-poly(methyl acrylate) by the Cu(0)/tris(2-dimethylaminoethyl)amine-catalyzed living radical polymerization and block copolymerization of methyl acrylate initiated with 1,1-chloroiodoethane and α,ω-Di(iodo)poly(vinyl chloride) in dimethyl sulfoxide (pages 1948–1954)

      Virgil Percec, Tamaz Guliashvili and Anatoliy V. Popov

      Version of Record online: 23 MAR 2005 | DOI: 10.1002/pola.20683

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      The ultrafast Cu(0)/tris(2-dimethylaminoethyl)amine (Me6-TREN)-catalyzed living radical polymerization of methyl acrylate (MA) initiated with 1,1-chloroiodoethane (CH3CHClI) at 25–70 °C and the living radical block copolymerization of MA initiated with α,ω-di(iodo)poly(vinyl chloride) at 25–90 °C in dimethyl sulfoxide (DMSO) are reported. The complete conversion of MA was achieved in reaction times, which depended on the temperature, of 3–30 min.

    20. “Radical-controlled” oxidative polymerization of phenol: Comparison with that of 4-phenoxyphenol (pages 1955–1962)

      Hideyuki Higashimura, Kiyoshi Fujisawa, Masaaki Kubota and Shiro Kobayashi

      Version of Record online: 23 MAR 2005 | DOI: 10.1002/pola.20647

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      “Radical-controlled” oxidative polymerization of phenol by (1,4,7-triisopropyl-1,4,7-triazacyclononane)copper(II) catalyst was performed. The coupling selectivity, reaction rate, reaction intermediate, polymerization behavior, and characterization of polymer were compared with those for 4-phenoxyphenol in detail.

    21. Kinetics of styrene emulsion polymerization above the critical micelle concentration: Effect of the initial monomer concentration on the molecular weight (pages 1963–1972)

      Jorge Herrera-Ordonez, Oscar Rivera, Hortensia Maldonado-Textle and Jorge C. Ramirez

      Version of Record online: 28 MAR 2005 | DOI: 10.1002/pola.20661

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      The emulsion polymerization of styrene above the critical micelle concentration has been experimentally studied from a low final polymer content up to a high polymer content (∼50%). Different possibilities, including some reported in the literature, are examined to explain the effect of the initial monomer concentration on the evolution of the molecular weight. It is proposed that, to a certain extent, the observed kinetic behavior originates from coagulative entry, for which the hydrodynamic conditions play important roles.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Study on kinetics of controlled/living radical polymerization of acrylonitrile by RAFT technique (pages 1973–1977)

      Quanfu An, Jinwen Qian, Liyun Yu, Yingwu Luo and Xinzhi Liu

      Version of Record online: 23 MAR 2005 | DOI: 10.1002/pola.20622

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      Polyacrylonitrile (PAN) was synthesized in DMF by RAFT employing azobis(isobutyronitrile) (AIBN) as the initiator and 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the chain transfer agent. The polymerization rate studied was directly proportional to [AIBN]0.94 and negative exponent to [CPDB], and a kinetic equation was obtained as Rp = k[AIBN]0.94[CPDB]−0.43[M] at 65 °C.

    2. Ethylene polymerization with silica-supported bis[3,5-dinitro-N-(2,6-diisopropylphenyl) salicylaldiminate]nickel(II)/methylaluminoxane catalysts (pages 1978–1984)

      Carlo Carlini, Alessio Ceccarini, Elizabeth Grillo Fernandes, Anna Maria Raspolli Galletti and Glauco Sbrana

      Version of Record online: 28 MAR 2005 | DOI: 10.1002/pola.20727

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      The anchoring of bis[3,5-dinitro-N-(2,6-diisopropylphenyl)salicylaldiminate]nickel(II) (I) to methylaluminoxane (MAO)-treated silica produced a thermally stable nickel-heterogenized catalyst able to polymerize ethylene into a high-molecular-weight linear polyethylene with higher productivity, in comparison with its homogeneous counterpart.

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