Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 10

15 May 2007

Volume 45, Issue 10

Pages 1801–2058

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
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      New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds (pages 1801–1813)

      Sadahito Aoshima, Tomohide Yoshida, Arihiro Kanazawa and Shokyoku Kanaoka

      Article first published online: 26 MAR 2007 | DOI: 10.1002/pola.21995

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      A variety of Lewis acid catalysts combined with appropriate weak bases led to unprecedented living reaction systems for the cationic polymerization of vinyl ethers: fast living polymerization within 1–3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe2O3. In addition, the base-stabilized living polymerization allowed the quantitative synthesis of star-shaped polymers with a narrow molecular weight distribution via polymer-linking reactions and the precision synthesis and highly sensitive self-assembly of stimuli-responsive block copolymers.

  2. Articles

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    2. Highlights
    3. Articles
    1. Fluorinated copolymers and terpolymers based on vinylidene fluoride and bearing sulfonic acid side-group (pages 1814–1834)

      L. Sauguet, B. Ameduri and B. Boutevin

      Article first published online: 29 MAR 2007 | DOI: 10.1002/pola.21978

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      The radical copolymerizations and terpolymerizations of vinylidene fluoride (VDF) with perfluoro(4-methyl-3,6-dioxaoct-7-ene sulfonyl fluoride (PFSVE) and hexafluoropropene, chlorotrifluoroethylene or bromotrifluoroethylene were investigated. The microstructures of the resulting copolymers were assessed by 19F NMR and their thermal properties (Tg and Td) investigated.

    2. Kinetic simulation of single electron transfer–living radical polymerization of methyl acrylate at 25 °C (pages 1835–1847)

      Michael J. Monteiro, Tamaz Guliashvili and Virgil Percec

      Article first published online: 26 MAR 2007 | DOI: 10.1002/pola.21947

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      Kinetic simulations demonstrated that activation rate by heterolytic outer-sphere single-electron transfer process responsible for SET-LRP is faster than by homolytic inner-sphere electron-transfer process responsible for ATRP, while deactivation rate is similar. In SET-LRP the Cu(II)X2/L deactivator is created by the disproportionation of Cu(I)X/L inactive species, while in ATRP its concentration is mediated by bimolecular termination. In SET-LRP, the combination of higher rate of activation with creation of deactivator by disproportionation mediates the ultrafast synthesis of polymers with very narrow molecular weight distribution, at room temperature, with a catalytic amount of Cu(0), and with virtually absent bimolecular termination.

    3. Build-up of carboxylic acids in polyethylene and their relation to off-flavor and carbonyl index (pages 1848–1859)

      Clara Strandberg and Ann-Christine Albertsson

      Article first published online: 26 MAR 2007 | DOI: 10.1002/pola.21948

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      Carboxylic acids are among the major degradation products of polyethylene (PE), and they are said to cause off-flavor in food and beverage packaging. The relation between carboxylic acids and off-flavor in water extracts of extruded PE and, between them and carbonyl index in thermally aged PE were investigated. The amount of the carboxylic acids was assessed by head-space solid-phase microextraction (HS-SPME) and gas chromatography-mass spectroscopy (GC-MS). The amount of butanoic and hexanoic acid correlated well with the rated off-flavor intensities in the water extracts of the extruded PE. In the thermally aged PE materials, propanoic acid was identified as an indicator product for earlier oxidation detection.

    4. Synthesis and characterization of a bis-(4-trifluoromethanesulfonyloxyphenyl)phenylamine monomer and its polymer for light-emitting applications (pages 1860–1867)

      Huseyin Zengin, Gulay Zengin, Chris M. Topping and Dennis W. Smith Jr.

      Article first published online: 29 MAR 2007 | DOI: 10.1002/pola.21950

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      The preparation, polymerization, characterization, and optical properties of a new bis-(4-trifluoromethanesulfonyloxyphenyl)phenylamine are reported. This is the first nitrogen-containing monomer having nitrogen atoms as bridges between phenyl rings, and it was synthesized in three steps. The structure of the monomer and its polymer were characterized with different spectroscopic techniques. The molecular weights were determined by gel permeation chromatography. The thermal behavior and stability of this polymer were investigated with thermogravimetric analysis, and the electrical conductivity of an HCl-doped film made from this new polymer was measured.

    5. Photolytic transformation of aryl benzobisoxazole and aryl benzobisthiazole compounds into carbon dioxide (pages 1868–1877)

      Ying-Hung So, Bruce M. Bell and Dave R. Albers

      Article first published online: 29 MAR 2007 | DOI: 10.1002/pola.21951

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      Solid-state aryl benzobisoxazole and aryl benzobisthiazole compounds photolyzed in the presence of O2 undergo cleavage to produce benzobisoxazoles (or benzobisthiazoles), benzonitriles, and benzamides. A very high percentage of carbon atoms in one of the segments from chain cleavage are converted to CO2. The rate of CO2 generation is used to compare the relative photostability of aryl benzobisoxazole and aryl benzobisthiazole model compounds, films, and fibers.

    6. High-molecular-weight AB-type benzoxazines as new precursors for high-performance thermosets (pages 1878–1888)

      Tarek Agag and Tsutomu Takeichi

      Article first published online: 29 MAR 2007 | DOI: 10.1002/pola.21953

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      A new approach to the preparation of benzoxazine resin was applied through the preparation of high-molecular-weight AB-type benzoxazine precursors. The precursors gave flexible, self-standing thin films after the casting and drying of their solutions at 60 °C, which are difficult to obtain with typical benzoxazine precursors. After the thermal treatment of the AB polybenzoxazine precursor films up to 250 °C, polybenzoxazine was obtained. Both viscoelastic and thermogravimetric analysis indicated that the thermosets derived from these novel AB precursors showed excellent thermomechanical properties as well as high thermal stability. This indicates that the approach of AB precursors is effective for obtaining novel polybenzoxazines with excellent properties.

    7. Synthesis of poly(L-lysine)-graft-polyesters through Michael addition and their self-assemblies in aqueous solutions (pages 1889–1898)

      Ning Xu, Fu-Sheng Du and Zi-Chen Li

      Article first published online: 29 MAR 2007 | DOI: 10.1002/pola.21949

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      Poly(L-lysine)-graft-poly(L-lactide) and poly(L-lysine)-graft-poly(ϵ-caprolactone) were synthesized through the Michael addition of poly(L-lysine) and maleimido-terminated poly(L-lactide) or poly(ϵ-caprolactone). These amphiphilic graft copolymers could self-assemble in an aqueous medium to form micelles or vesicles, depending on the grafting density of poly(ϵ-caprolactone) to poly(L-lysine).

    8. Synthesis, characterization and photoinduction of optical anisotropy in liquid crystalline diblock azo-copolymers (pages 1899–1910)

      P. Forcén, L. Oriol, C. Sánchez, R. Alcalá, S. Hvilsted, K. Jankova and J. Loos

      Article first published online: 3 APR 2007 | DOI: 10.1002/pola.21954

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      Block copolymers, synthesized by ATRP and having azo units confined in nano-domains, exhibits photo-orientational properties similar to the corresponding homopolymer. Dilution of azo content with respect to homopolymers makes these materials attractive for volume holography.

    9. Coating lysozyme molecularly imprinted thin films on the surface of microspheres in aqueous solutions (pages 1911–1919)

      Chang-Ling Yan, Yan Lu and Shu-Yan Gao

      Article first published online: 3 APR 2007 | DOI: 10.1002/pola.21955

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      In aqueous solutions containing templates, thin films of poly(3-aminophenylboronic acid) (poly-APBA) were grafted onto polystyrene (PS) microspheres, and the template molecules simultaneously combined with poly-APBA. After the PS microspheres with poly-APBA were washed, the template molecules were removed, and the produced sites had the ability to recognize the template molecules when rebinding was carried out.

    10. Crosslinking of a polyacrylate bearing a spiroorthoester pendant group with mixtures of diglycidyl ether of bisphenol A and phosphorus-containing glycidyl derivatives (pages 1920–1930)

      J. Canadell, A. Mantecón and V. Cádiz

      Article first published online: 3 APR 2007 | DOI: 10.1002/pola.21956

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      The cationic crosslinking of a polyacrylate bearing a spiroorthoester pendant group with mixtures of diglycidyl ether of bisphenol A and three phosphorus-containing glycidyl derivatives was carried out with ytterbium triflate as an initiator. The curing process was monitored with Fourier transform infrared spectroscopy. The incorporation of phosphorus into the network increased the limiting oxygen index values, thus improving the flame retardancy of the materials. During crosslinking, all the crosslinked polymers showed slight shrinkage that was much lower than that observed in conventional epoxy resins.

    11. Depolymerization kinetics of di(4-tert-butyl cyclohexyl) itaconate and Mark-Houwink-Kuhn-Sakurada parameters of di(4-tert-butyl cyclohexyl) itaconate and di-n-butyl itaconate (pages 1931–1943)

      Zachary Szablan, Ming Huaming, Martina Adler, Martina H. Stenzel, Thomas P. Davis and Christopher Barner-Kowollik

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21957

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      The Mark Houwink Kuhn Sakurada parameters for di-n-butyl itaconate and di(4-tert-butylcyclohexyl) itaconate in THF at 40°C were determined using a triple detection size exclusion chromatography setup. Multipulse pulsed laser polymerization coupled with size exclusion chromatography was employed to determine the effective propagation rate coefficients for di(4-tert-butylcyclohexyl) itaconate in anisole over a wide temperature range. The determined Mark Houwink Kuhn Sakurada parameters for di(4-tert-butylcyclohexyl) itaconate allowed for the determination of accurate Arrhenius parameters for the forward propagation reaction, with kinetic data obtained in the temperature region where depolymerization was unable to be neglected, allowing for an estimation of the ceiling temperature in solution using a fit optimization procedure.

    12. Synthesis and characterization of poly(L-lactide)s and poly(D-lactide)s of controlled molecular weight (pages 1944–1955)

      Matthieu Jalabert, Carole Fraschini and Robert E. Prud'homme

      Article first published online: 4 APR 2007 | DOI: 10.1002/pola.21960

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      A series of optically pure poly(L-lactide)s and poly(D-lactide)s have been synthesized by controlled ring-opening polymerization. A kinetic study shows that intermolecular transesterification reactions occur at the very beginning of the polymerization and increase with time. These reactions can be studied by MALDI-TOF mass spectrometry with the emergence of a distribution characterized by chains with an odd-number of lactic acid repeat units.

    13. Synthesis of oligomeric urethane dimethacrylates with carboxylic groups and their testing in dental composites (pages 1956–1967)

      Emil C. Buruiana, Tinca Buruiana, Violeta Melinte, Mirela Zamfir, Aurora Colceriu and Marioara Moldovan

      Article first published online: 4 APR 2007 | DOI: 10.1002/pola.21959

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      Four urethane dimethacrylates containing poly(ethylene oxide) sequences and carboxylic acid for improving adhesiveness were synthesized and characterized. For the preparation of dental formulations, a similar urethane dimethacrylate oligomer that did not contain carboxyl groups was prepared and used as a comonomer with reduced viscosity to establish a correlation between the structure and the behavior for photopolymerization. The obtained dependence could be used for the precise characterization of the degree of the photocuring reaction in oligomer-based dental formulations by fluorescence spectroscopy. The influence of the carboxyl content and the resin composition on the adhesive properties and polymerization shrinkage was investigated. The diametral tensile and flexural strengths were also determined.

    14. New thermosets obtained by the cationic copolymerization of diglycidyl ether of bisphenol A with γ-caprolactone with an improvement in the shrinkage. I. Study of the chemical processes and physical characteristics (pages 1968–1979)

      Servando González, Xavier Fernández-Francos, Josep Maria Salla, Angels Serra, Ana Mantecón and Xavier Ramis

      Article first published online: 4 APR 2007 | DOI: 10.1002/pola.21961

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      Mixtures of diglycidyl ether of bisphenol A and γ-caprolactone with different proportions were cured with ytterbium triflate as an initiator. Fourier transform infrared spectroscopy was used to monitor the competitive reactive processes and to quantify the conversions of the epoxide, lactone, and intermediate spiroorthoester groups. A partial depolymerization process from the cured material to free γ-caprolactone was also identified. An increase in the proportion of γ-caprolactone resulted in an increased curing rate, a decrease in the shrinkage after gelation, and a significant decrease in the glass transition temperature. The introduction of ester linkages in the network increased the thermal degradability of the materials.

    15. Synthesis of a novel bis-spiroorthoester containing 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide as a substituent: Homopolymerization and copolymerization with diglycidyl ether of bisphenol A (pages 1980–1992)

      J. Canadell, A. Mantecón and V. Cádiz

      Article first published online: 4 APR 2007 | DOI: 10.1002/pola.21962

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      A new bis-spiroorthoester-containing monomer, bis[(1,4,6-trioxaspiro-[4.4]-nonan-2-yl)-methyl] 2-[10-(9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide-10-yl)] maleate (SOE-DOPOMA), was synthesized. SOE-DOPOMA was characterized with 1H, 13C, and 31P NMR spectroscopy and was crosslinked with ytterbium triflate as a cationic initiator. A mixture of SOE-DOPOMA and diglycidyl ether of bisphenol A was also crosslinked under the same conditions. The curing was studied with differential scanning calorimetry, thermogravimetric analysis, and thermodynamomechanical analysis and monitored with Fourier transform infrared spectroscopy. The shrinkage effects on crosslinking and the flame-retardant properties were determined.

    16. Living anionic polymerization of 2-vinyldibenzothiophene: Homopolymer and block copolymers with styrene (pages 1993–2003)

      A. Avila-Ortega and H. Vázquez-Torres

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21965

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      Anionic polymerization of 2-vinyldibenzothiophene and its copolymerization with styrene was accomplished by using n-BuLi in benzene at 30 °C. The living character of these polymerizations was stated with basis on the linearity showed by the plot of ln([M]0/[M]) with time (i.e. there is no chain termination) and supplemented by the criterion for the linearity of Mn with conversion (i.e. there is no chain transfer). The reactivity ratios were r2VDBT = 1.11 and rSt = 0.49 (Kélen–Tüdös) and r2VDBT = 1.05 and rSt = 0.50 (Joshi–Joshi). The value r2VDBTxrSt = 0.54 (K–T) or 0.52 (J–J) indicates comonomers alternation.

    17. Synthesis and electrochromism of novel organosoluble polyarylates bearing triphenylamine moieties (pages 2004–2014)

      Guey-Sheng Liou, Cha-Wen Chang, Huang-Ming Huang and Sheng-Huei Hsiao

      Article first published online: 11 APR 2007 | DOI: 10.1002/pola.21966

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      A series of novel aromatic polyarylates with triphenylamine units in main chain and as the pendent group were prepared from the dicarboxylic acid monomer, N,N-bis(4-carboxyphenyl)-N′,N′-diphenyl-1,4-phenylenediamine (1), and various bisphenols. These polyarylates were amorphous and readily soluble in common organic solvents. They had excellent levels of thermal stability associated with moderately high Tg values. These anodically polymeric electrochromic materials not only showed reversible electrochromic stability with good green coloration efficiency (CE = 159 cm2/C) and blue coloration efficiency (CE = 154 cm2/C) but also exhibited high contrast of optical transmittance change (ΔT%), 54% in 895 nm for green color and (ΔT%) and up to 84% in 595 nm for blue color. After over 100 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics. [Color figure can be viewed in the online issue, which is available at]

    18. A bidirectional ATRP-NMRP initiator: The effect of nitroxide size on the rate of nitroxide-mediated polymerization (pages 2015–2025)

      Jean Ruehl and Rebecca Braslau

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21967

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      An asymmetric double-headed initiator containing both an α-bromoester and an N-alkoxyamine functionality was synthesized. Atom transfer radical polymerization (ATRP) was used to grow a polymer from the α-bromoester end of this initiator. In an orthogonal process, nitroxide mediated radical polymerization (NMRP) was used to grow a polymer from the N-alkoxyamine end of this macroinitiator. The polymerization kinetics were investigated, and it was found that the rate of polymerization was unaffected by the size of the macromolecular nitroxide cap.

    19. Synthesis and characterization of novel liquid-crystalline copolymers containing thermally stable photochromic groups (pages 2026–2037)

      Jui-Hsiang Liu, Po-Chih Yang, Yi-Hong Chiu and Yasuo Suda

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21968

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      The photoisomerization of configurational E/Z structures was investigated with an ultraviolet–visible spectrophotometer with 300-nm ultraviolet irradiation. The thermal stability of the Z-structural segment in the polymers was confirmed through the heating of the polymer at 70 °C for over 10 h. This investigation demonstrated that the liquid-crystal phases and phase-transition temperatures of the compounds depended on the molecular structure. Both the polarity of the center part and the molecular length at the ends of the molecules were found to be necessary factors for the formation of liquid-crystalline molecules. The picture shows a real image recording of a liquid-crystal cell fabricated in this investigation with ultraviolet irradiation through a mask with the words written therein.

    20. Polymerization of conjugated 5-[(5-ethynyl-1-naphthyl)ethynyl]-N,N-dimethylnaphthalen-1-amine with rhodium and palladium complexes (pages 2038–2047)

      J. Gonzalo Rodríguez and Jose Luis Tejedor

      Article first published online: 10 APR 2007 | DOI: 10.1002/pola.21969

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      The monomer 5-[(5-ethynyl-1-naphthyl)ethynyl]-N,N-dimethylnaphthalen-1-amine was satisfactory obtained through the heterocoupling reaction of 5-ethynyl-N,N-dimethylnaphthalen-1-amine and 4-(5-iodo-1-naphthyl)-2-methyl-3-butyn-2-ol catalyzed by a palladium–copper system, followed by acetone elimination. Poly{5-[(5-ethynyl-1-naphthyl) ethynyl]-N,N-dimethylnaphthalen-1-amine} was obtained through the reaction of the acetylene monomer with homogeneous rhodium and palladium catalyst complexes. The structure of the polymers always showed a trans–cisoidal chain configuration on the basis of IR and NMR spectra. Moreover, only for the rhodium catalyst complex in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain-transfer intermediate in the polymer propagation. The mass determination of the polymers, by osmometry and gel permeation chromatography techniques, showed low average molecular weights. The kinetics of the catalyzed polymerization were analyzed.

    21. Synthesis and optical properties of light-emitting π-conjugated polymers containing biphenyl and dithienosilole (pages 2048–2058)

      Liang Liao, Ali Cirpan, Qinghui Chu, Frank E. Karasz and Yi Pang

      Article first published online: 9 APR 2007 | DOI: 10.1002/pola.21970

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      Copolymers containing oligo(phenylene vinylene), fluorene, and dithienosilole units were synthesized and characterized. Double-layer light-emitting-diode devices using these polymers had relatively low turn-on voltages (3.5–4 V). The results show that dithienosilole plays a positive role in improving the charge-injection characteristics of poly(phenylene vinylene) materials.