Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 14

15 July 2004

Volume 42, Issue 14

Pages 3395–3653

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
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      Stereospecific polymerization of methacrylates by metallocene and related catalysts (pages 3395–3403)

      Eugene Y.-X. Chen

      Version of Record online: 1 JUN 2004 | DOI: 10.1002/pola.20184

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      Stereospecific—isospecific, syndiospecific, and diastereospecific—polymerizations of methacrylates using group 4 metallocene and related catalysts produce polymethacrylates with programmable stereo-microstructures.

  2. Articles

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    2. Highlights
    3. Articles
    4. Rapid Communications
    1. Grafting of dodecyl methacrylate onto hydroxylated polybutadiene by miniemulsion polymerization (pages 3404–3416)

      Thi Thuy Binh Pham, Christopher M. Fellows and Robert G. Gilbert

      Version of Record online: 1 JUN 2004 | DOI: 10.1002/pola.20131

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      Homogeneous copolymer latex particles of dodecyl methacrylate (DMA) and low-molecular-weight hydroxy-terminated polybutadiene (HTPB) oligomers were prepared by free-radical polymerization using miniemulsion methods. Characterization of the copolymer latex particles using transmission electron microscopy (TEM) and modulated differential scanning calorimetry suggested that there is a significant amount of grafted poly(DMA)/HTPB polymer contributing to the miscibility of the HTPB and poly(DMA) phases. Particles were more homogeneous at increased HTPB composition, of relatively narrow polydispersity, and could be prepared reproducibly using a number of different initiation systems. The observed trends can all be rationalized in terms of conventional understanding of miniemulsion polymerization systems.

    2. Synthesis and nuclear magnetic resonance analysis of starch-g-poly(1,4-dioxan-2-one) copolymers (pages 3417–3422)

      Xiu-Li Wang, Ke-Ke Yang, Yu-Zhong Wang, Zhi-Xuan Zhou and Yong-Dong Jin

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20203

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      Starch-g-poly(1,4-dioxan-2-one) was synthesized through the ring-opening graft polymerization of 1,4-dioxan-2-one onto a starch backbone. The grafting reactions were conducted with various 1,4-dioxan-2-one/starch feed ratios to obtain starch-g-poly(1,4-dioxan-2-one) copolymers with various poly(1,4-dioxan-2-one) graft structures, which were characterized with one- and two-dimensional NMR spectroscopy.

    3. Physicochemical characterization of α-chitin, β-chitin, and γ-chitin separated from natural resources (pages 3423–3432)

      Mi-Kyeong Jang, Byeong-Gi Kong, Young-Il Jeong, Chang Hyung Lee and Jae-Woon Nah

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20176

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      Chitin separated from natural resources has three polymorphic crystalline structures: α, β, and γ. The physicochemical properties of chitin are differently presented according to these structures. The properties of α-chitin and β-chitin have been observed by many investigators, but those of γ-chitin, first proposed by Rudall et al., have not been revealed until now because of the unusual nature of the raw material. In this study, γ-chitin has been separated and characterized. Also, the properties of α-chitin and β-chitin have been compared with those of γ-chitin.

    4. The influence of comonomer (2-hydroxyethyl acrylate) and keto group on photocrosslinking property of arylidene polymers (pages 3433–3444)

      A. Arun and B. S. R. Reddy

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20196

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      The effect of comonomer and the keto group on the rate of photocrosslinking of the arylidene polymers was studied extensively. The possible reasons for the enhancement in the rate of photocrosslinking were discussed. Reactivity ratios of the monomers were evolved using available graphical methods to find out the number of comonomer units apart from the arylidene monomer units present in the copolymer chain.

    5. Synthesis of azobenzene-containing polythiophenes and photoinduced anisotropy (pages 3445–3455)

      Francois Aubertin and Yue Zhao

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20115

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      Three polythiophenes containing an azobenzene group in the side-chain were synthesized and characterized. The investigation of photoinduced anisotropy in two polymers by irradiation with an Ar+ laser at 488 nm finds that unlike other amorphous azobenzene polymers, only an extremely small anisotropy can be optically obtained in these azobenzene polythiophenes.

    6. Synthesis of di- and tetra-adducts by addition of polystyrene macroradicals onto fullerene C60 (pages 3456–3463)

      Fabrice Audouin, Richard Nuffer and Claude Mathis

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20201

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      Br-terminated polystyrenes of controlled molar masses and low polydispersities prepared by ATRP were converted to macro-radicals using an appropriate catalytic complex (CuBr/bipyridine/100 °C) in the presence of C60. The addition of the macroradicals PS° to 6–6 bonds of the fullerene follows a specific atom transfer radical addition mechanism that favors the grafting of even numbers of chains onto the fullerene core. This offers an easy synthetic route toward well-defined di- and tetra-adducts. To form these adducts only one and two double bonds, respectively, are converted to single bonds, keeping the disturbance of the electronic structure of the fullerene at its minimum.

    7. Kinetic modeling studies of ethylene polymerization reactions using supported chromium catalysts (pages 3464–3472)

      I. Matos, Y. Zhang, M. A. N. D. A. Lemos, Filipe Freire, I. F. Fonseca, M. M. Marques and F. Lemos

      Version of Record online: 8 JUN 2004 | DOI: 10.1002/pola.20204

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      The kinetics of ethylene polymerization reactions with chromium-supported catalysts in silica, zeolite, and charcoal were studied. A kinetic model based on a proposed mechanism for these reactions was used to fit the experimental data.

    8. Aliphatic–aromatic copolyesters derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (pages 3473–3478)

      Nathan C. Hoppens, Todd W. Hudnall, Adam Foster and Chad J. Booth

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20197

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      2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) is an aliphatic diol monomer that has been incorporated into both polycarbonates and polyesters. This article reports the thermal data obtained from a series of random poly(CBCO/Bisphenol)terephthalates. These polymers have Tg's around 200 °C and Td's near 400 °C.

    9. Synthesis, characterization, and emulsion polymerization of polymerizable coumarin derivatives (pages 3479–3489)

      Jung Kwon Oh, Valentina Stöeva, Jude Rademacher, Rajeev Farwaha and Mitchell A. Winnik

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20148

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      The new polymerizable coumarin derivative [6-(β-acryloxyethoxy)-7-isopropoxy-4-methyl coumarin (3)] was synthesized. Its UV absorption spectrum significantly overlaps the emission spectrum of the 9-alkyl phenanthrene (1). This dye can serve several purposes in latex films. It can be a tracer for fluorescence microscopy experiments, or it can act as a donor or acceptor dye in non-radiative energy transfer experiments. Coumarin-labeled poly(butyl methacrylate) (PBMA) latex dispersions could be synthesized by conventional batch emulsion polymerization with complete monomer conversion and dye incorporation, and uniform dye distribution.

    10. Preparation and thermomechanical properties of epoxy resins modified by octafunctional cubic silsesquioxane epoxides (pages 3490–3503)

      Khine Yi Mya, Chaobin He, Junchao Huang, Yang Xiao, Jie Dai and Yeen-Ping Siow

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20168

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      The epoxy functionalized POSS were synthesized and used as reinforcing additives to improve thermomechanical properties of standard epoxy resin by exploring the effects of varying the molar ratios of POSS epoxy to standard epoxy. The glass-transition temperature exhibiting from the tan delta curve was disappeared in addition of 20 mol % of POSS epoxy to the standard epoxy resin. It indicates the prohibition of segmental chain motion in the presence of a rigid cubic structure of silsesquioxane and implies that the POSS-modified epoxy resins are good thermal-mechanical property modifiers.

    11. Synthesis of a series of SG1 2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxyl] based alkoxyamines, SG1-CH(Me)CO2R, and measurement of the homolysis rate constants of the C[BOND]ON bond (pages 3504–3515)

      D. Bertin, D. Gigmes, S. Marque, R. Maurin and P. Tordo

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20178

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      During nitroxide-mediated polymerization, the polymerization time decreases with an increasing rate constant of the cleavage of the NO[BOND]C bond of dormant alkoxyamines. Thus, knowledge of the factors influencing this cleavage is of considerable interest. We have prepared a series of SG1 2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxyl] based alkoxyamines [SG1-CH(Me)CO2R] with various R groups (alkyl or aryl) and measured the homolysis rate constants (kd). kd decreases with the bulkiness and increases with the polarity of the R group.

    12. Novel flame-retardant thermosets: Phosphine oxide-containing diglycidylether as curing agent of phenolic novolac resins (pages 3516–3526)

      M. A. Espinosa, M. Galià and V. Càdiz

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20220

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      Phosphorus-containing novolac–epoxy systems were prepared from novolac resins and isobutyl bis(glycidylpropylether) phosphine oxide (IHPOGly) as crosslinking agent. The Tg and decomposition temperatures of the resulting thermosets are moderate and decrease when the phosphorous content increases. Whereas the phosphorous species decrease the thermal stability, at higher temperatures the degradation rates are lower than the degradation rate of the phosphorous-free resin. V-O materials were obtained when the resins were tested for ignition resistance with the UL-94 test.

    13. Synthesis of end-functionalized AB copolymers. II. Synthesis and characterization of carboxyl-terminated poly(ethylene glycol)–poly(amino acid) block copolymers (pages 3527–3536)

      Sheng Zhang, Jie Qing, Chengdong Xiong and Yuxing Peng

      Version of Record online: 7 JUN 2004 | DOI: 10.1002/pola.20078

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      AB block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(amino acid) with a carboxyl group at the end of PEG were synthesized with α-carboxylic sodium-ω-amino-PEG as a macroinitiator for the ring-opening polymerization of N-carboxy anhydride. Characterizations by 1H NMR, IR, and gel permeation chromatography were carried out to confirm that the diblock copolymers were formed. In aqueous media this copolymer formed self-associated polymer micelles that have a carboxyl group on the surface. The carboxyl groups located at the outer shell of the polymeric micelle were expected to combine with ligands to target specific cellpopulations. The diameter of the polymer micelles was in the range of 30–80 nm.

    14. Macromolecular surfactants for supercritical carbon dioxide applications: Synthesis and characterization of fluorinated block copolymers prepared by nitroxide-mediated radical polymerization (pages 3537–3552)

      Patrick Lacroix-Desmazes, Pascal Andre, Joseph M. Desimone, Anne-Valérie Ruzette and Bernard Boutevin

      Version of Record online: 8 JUN 2004 | DOI: 10.1002/pola.20193

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      Poly(perfluorooctyl-ethylenoxymethylstyrene) (PFDS) and poly (1,1,2,2-tetrahydroperfluorodecyl acrylate) (PFDA) homopolymers as well as poly(styrene)-b-PFDS and poly(styrene)-b-PFDA CO2-phobic/CO2-philic block copolymers of various chain lengths were synthesized by nitroxide-mediated radical polymerization. The effect of the composition and molecular weight of the polymers on their solution properties in supercritical CO2 has been studied. Additionally, surface and bulk characterizations of PS-b-PFDA indicated the same surface tension as for the PFDA homopolymer (γLV = 10.3 mN/m) and a bulk nanostructured morphology.

    15. A new tetradentate ligand for atom transfer radical polymerization (pages 3553–3562)

      Shijie Ding, Youqing Shen and Maciej Radosz

      Version of Record online: 8 JUN 2004 | DOI: 10.1002/pola.20218

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      The new tetradentate ligand forms complexes with cooper halide having fast activation reactions in ATRP. The CuCl/BPED is thus highly active for ATRP of methyl acrylate and styrene, but the activation reaction of CuBr/BPED is so fast that most of CuBr is consumed to produce CuBr2. The comparison with other tetradentate ligands suggests that the pyridine units in the ligand favor the catalyst's activation reaction.

    16. Synthesis of narrow-polydispersity degradable dendronized aliphatic polyesters (pages 3563–3578)

      Cameron C. Lee, Scott M. Grayson and Jean M. J. Fréchet

      Version of Record online: 8 JUN 2004 | DOI: 10.1002/pola.20216

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      The divergent dendronization of a functionalized poly(ϵ-caprolactone) affords fourth-generation dendronized polymers with molecular weights as high as 80,000 Da and typical polydispersities between 1.1–1.2 with sufficient biocompatibility and biodegradability for use as drug-delivery scaffolds.

    17. The kinetics of the epoxy amine cure reaction from a solvation perspective (pages 3579–3586)

      James D. R. Talbot

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20219

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      The kinetics of the cure reaction of epoxy–amine thermosets has been explained and predicted based on a solvation model allowing for hydrogen bonding of the amine nucleophile with other molecules of the amine hardener. Hydrogen bonding with other the species present — epoxy and product/hydroxy groups — was not required to account for the commonly observed form of the rate equation of these reactions: ∂α/∂t = (k1 + k2αm)(1 − α)n. The model predicted 1 > m >2/3 and 2 > n > 1 as is often found. No starter reaction was required to explain the presence of k1.

    18. Synthesis and photoluminescence of linear and hyperbranched polyethers containing phenylquinoxaline units and flexible aliphatic spacers (pages 3587–3603)

      Jong-Beom Baek and L.-C. Chien

      Version of Record online: 8 JUN 2004 | DOI: 10.1002/pola.20163

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      Several fluorescent linear and hyperbranched polyethers containing phenylquinoxaline units and flexible aliphatic spacers were prepared. A hyperbranched polyether containing a phenylquinoxaline moiety, prepared from the AB2 monomer 2,3-bis(6-bromohexyloxyphenyl)-6-(4-hydroxyphenyloxy)quinoxaline, exhibited fluorescence maxima at 436 nm with a relatively narrow bandwidth.

    19. Synthesis of poly(vinylene arsine)s through the ring-collapsed radical alternating copolymerization of an organoarsenic homocycle with aliphatic acetylenes and their properties (pages 3604–3611)

      Tomokazu Umeyama, Kensuke Naka and Yoshiki Chujo

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20240

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      We describe here the synthesis of poly(vinylene arsine)s with no aromatic substituent through the ring-collapsed radical alternating copolymerization of cyclooligoarsine with aliphatic acetylenes with 2,2′-azobisisobutyronitrile as a radical initiator or through irradiation with an incandescent lamp. The number-average molecular weights of the copolymers were estimated to be in the range of thousands by gel permeation chromatography analysis. The 1H NMR and 13C NMR spectra of the copolymer revealed that the copolymerization proceeded in a highly alternating fashion. By gas chromatography analysis, the reactivity of aliphatic acetylene toward the arsenic homocycle was found to be much lower than that of phenylacetylene because of the lack of conjugative substitution.

    20. Structure–property correlations of sulfonated polyimides. I. Effect of bridging groups on membrane properties (pages 3612–3620)

      Choonkeun Lee, Saimani Sundar, Jinuk Kwon and Haksoo Han

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20214

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      Sulfonated polyimide membranes with increasing bulkiness of the bridging groups were synthesized. The conductivity at high temperature increased exponentially for polyimides. The high conductivity over Nafion®115 at high temperature is attributed to the increased free volume. It was also found that the hydrolytic stability of the polyimides with bulky bridging groups is higher.

    21. Structure–property correlations of sulfonated polyimides. II. Effect of substituent groups on membrane properties (pages 3621–3630)

      Choonkeun Lee, Saimani Sundar, Jinuk Kwon and Haksoo Han

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20215

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      Sulfonated polyimides with alkyl substituents were synthesized. The conductivity at high temperature was dramatically improved for substituted polyimides despite low ion exchange capacity, which is proposed to be due to the increasing free volume. The hydrolytic stability of substituted imides were also very high because of high nucleophilicity of the diamine due to electron pumping by the alkyl groups and increased flexibility of the polyimide chains.

    22. Liquid-crystalline thermosets from liquid-crystalline epoxy resins containing bisazomethinebiphenylene mesogens in the central core: Copolymerization with a nonmesomorphic epoxy resin (pages 3631–3643)

      Pere Castell, Angels Serra and Marina Galià

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20254

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      A new series of liquid-crystalline epoxy resins was synthesized, and their mesomorphic behavior was investigated. These glycidylic compounds had central aromatic imine mesogens derived from benzidine and aliphatic spacers of up to 10 methylene units. Crosslinking these monomers with primary aromatic diamines led to nematic networks, some of which contained crystal inclusions. However, through curing with tertiary amines as catalytic agents or through copolymerization with different proportions of the nonmesomorphic epoxy monomer and primary amines as crosslinking agents, smectic C or nematic thermosets were prepared depending on the number of methylene units of the spacers.

  3. Rapid Communications

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    2. Highlights
    3. Articles
    4. Rapid Communications
    1. Synthesis of functionalized macroinimer by N,N-diethyldithiocarbamate-mediated living free-radical polymerization (pages 3644–3648)

      Koji Ishizu, Hirokazu Kakinuma and Jaebum Park

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20194

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      We presented a one-pot approach to functionalized macroinimer via living free-radical polymerization. The living free-radical copolymerization of the mixture of (N,N-diethyldithiocarbamyl)methyl styrene (DTCS), maleic anhydride (MA), and styrene (100:10 equiv mixture of styrene and MA) was studied in tetrahydrofuran under UV irradiation. The formation of alternating sequences was initially fast with preferential consumption of styrene and MA. Further polymerization involved growth of a homopolystyrene block.

    2. Living cationic polymerization of vinyl ethers with a tricyclodecane or tricyclodecene unit: Synthesis of new poly(vinyl ether)s with high glass-transition temperature (pages 3649–3653)

      Takeshi Namikoshi, Tamotsu Hashimoto and Toshiyuki Kodaira

      Version of Record online: 9 JUN 2004 | DOI: 10.1002/pola.20224

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      The polymerizations of vinyl ethers with a tricyclodecane or tricyclodecene unit (1, 2, and 3) with the HCl/ZnCl2 initiating system in toluene at −30 °C proceeded in a living manner to give high molecular-weight polymers with controlled molecular weights and narrow molecular weight distributions. The Tg's of poly(1) and poly(2) reached ∼100 °C, whereas the Tg of poly(3) was lower than those of poly(1) and poly(2), but still much higher than room temperature. These results show that the rigid tricyclic groups in the side chains effectively elevate the Tg of poly(vinyl ethers)s.

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