Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 1

1 January 2006

Volume 44, Issue 1

Pages 1–696

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      Development of organotellurium-mediated and organostibine-mediated living radical polymerization reactions (pages 1–12)

      Shigeru Yamago

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21154

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      Polymer-end mimetic organotellurium and organostibine compounds mediate highly controlled living radical polymerizations that allow the molecular weight to be controlled accurately and give well-defined end groups. A variety of both conjugated and unconjugated monomers have been successfully polymerized in a controlled manner. AB diblock, ABA triblock, and ABC triblock copolymers have also been synthesized by the successive addition of different monomers.

  2. Articles

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    3. Articles
    4. Rapid Communications
    5. Note
    6. Notes
    1. Synthesis of phosphonated copolymers with tailored architecture by reversible addition-fragmentation chain transfer polymerization (RAFT) (pages 13–24)

      Bérengère Rixens, Romain Severac, Bernard Boutevin and Patrick Lacroix-Desmazes

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.20990

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      The synthesis by RAFT polymerization of three phosphonated terpolymers with tailored architecture has been studied. Thus, a gradient terpolymer poly(vinylidene chloride-co-methyl acrylate-co-phosphonated methacrylate), a statistical terpolymer poly(vinylidene chloride-co-methyl acrylate-co-hydroxyethyl acrylate) or poly(VC2-co-MA-co-HEA), and a diblock terpolymer poly(VC2-co-MA)-b-poly(HEA) were prepared, the last two terpolymers being subsequently modified through the hydroxyl groups of HEA units by reaction with a phosphonated epoxide.

    2. Abilities of 2-arylmethyloxy-6-cyanonaphthalene derivatives to initiate radical and cationic photopolymerizations (pages 25–31)

      Kenta Tanaka, Ryoichi Akimoto, Tetsutaro Igarashi and Tadamitsu Sakurai

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21135

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      Excited-state 2-(9-anthrylmethyloxy)-6-cyanonaphthalene undergoes homolytic Ar[BOND]OCH2 bond cleavage and heterolytic ArO[BOND]CH2 bond cleavage to give the corresponding radical-pair and ion-pair intermediates. An inspection of the radical and cationic photopolymerization behavior observed in the presence of some aryl-substituted 2-naphthols led us to conclude that the 9-anthrylmethyl-substituted 2-naphthol derivative is a candidate for a functional hybrid-type photoinitiator containing no halogen and/or metal.

    3. Atom transfer radical polymerization of styrene using the novel initiator ethyl 2-N,N-(diethylamino)dithiocarbamoyl-butyrate (pages 32–41)

      Wei Zhang, Xiulin Zhu, Jian Zhu and Jianying Chen

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21130

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      Well-defined polystyrene bearing a photo-labile N,N-(diethylamino)dithiocarbamoyl group was successfully synthesized with ethyl 2-N,N-(diethylamino)dithiocarbamoyl-butyrate as a novel initiator via atom transfer radical polymerization. The polymerization rate was first-order with respect to the monomer concentration, and the molecular weights of the obtained polymers increased linearly with the monomer conversions with very narrow molecular weight distributions; this indicated the living/controlled nature of the polymerization.

    4. Synthesis and liquid crystalline properties of new amide-modified poly(1,4-cyclohexanedimethylene terephthalate) (pages 42–52)

      P. Deepa, K. Divya and M. Jayakannan

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21062

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      We have demonstrated a ester-amide approach for introducing nematic liquid crystalline property in a commercially important cycloaliphatic polyester such as poly(1,4-cyclohexanedimethyleneterephthalate). The poly(esteramide)s were synthesized by solution condensation routes, and their structures and compositions are confirmed by NMR and FTIR spectroscopy. The nematic liquid crystalline domains formed by the ester-amide linkages increases the polymer chain alignment for higher Tg and also enhance the nucleation of the polymer crystallization for higher percent crystallinity. [A color version of the adjacent figure can be viewed in the online issue, which is available at www. interscience. wiley.com.]

    5. Photoactive, liquid-crystalline, hyperbranched benzylidene polyesters: Synthesis and characterization (pages 53–61)

      M. Murali and A. B. Samui

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21118

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      A photoactive, liquid-crystalline, hyperbranched benzylidene polyester (PAHBP) was synthesized, and its properties were thoroughly investigated. PAHBP showed a nematic mesophase over a wide range of temperatures, and its degree of branching was 0.53. The presence of the linear, rod-shaped, E-E-isomeric structure of the bisbenzylidene cyclohexanone units induced the mesophase. The photoresponsive nature, studied under ultraviolet light, exhibited photocrosslinking.

    6. TEMPO-mediated dispersion polymerization of styrene in the presence of camphorsulfonic acid (pages 62–68)

      Sejin Oh, Kijung Kim, Byung H. Lee, Sang Eun Shim and Soonja Choe

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.20988

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      The TEMPO-mediated polymerization of styrene in the presence of camphorsulfonic acid (CSA) is carried out using controlled radical dispersion polymerization. The experimental result obviously indicates that the addition of CSA in TEMPO-mediated dispersion polymerization not only shortens the polymerization time but also greatly improves the uniformity of the microspheres.

    7. Control of the conjugation length and solubility in electroluminescent polymers (pages 69–76)

      David A. Stone, Youngkyu Chang and Harry R. Allcock

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21140

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      Poly(phenylenevinylene-alt-cyclotriphosphazene)s were synthesized through the Heck coupling reaction. The polymer structure isolated each chromophore to break the conjugation. This allowed careful tuning of the band-gap energy and emission wavelength. Substitution on the phosphazene for increased solubility had no effect on the electronic properties of the polymers.

    8. Air-stable and recoverable catalyst for copper-catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction (pages 77–87)

      Gurkan Hizal, Umit Tunca, Sermin Aras and Humeyra Mert

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21048

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      Copper-catalyzed LRP of styrene (St) was conducted using the silica gel-supported CuCl2/PMDETA (SG-CuCl2/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on the in situ generation and regeneration of Cu(I) via electron transfer reaction between phenol derivative and Cu(II). Sodium phenoxide or p-methoxy phenol was used as a reducing agent of Cu(II) complexes in LRP of St.

    9. Behavior of nitroxyl radical in the polymerization process forming copolymers bearing diarylnitrone pendants and photocontrol of refractive indices for these copolymers (pages 88–97)

      Kenta Tanaka, Emi Takayanagi, Tetsutaro Igarashi and Tadamitsu Sakurai

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21138

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      To establish the reaction condition under which the radical copolymerization of α-(2-hydroxy-4-methacryloyloxyphenyl)-N-(2,6-dimethylphenyl)nitrone (HMDN) proceeds smoothly to give photoreactive copolymers, the effects of the nitrone chromophore on the radical polymerization behavior were investigated. This polymerization condition allowed us to prepare the HMDN/methyl methacrylate, HMDN/styrene, and HMDN/cyclohexyl acrylate copolymers in good yields. The photoirradiation of the copolymer film prepared on a silicon wafer lowered its refractive index by 0.003–0.023, depending on the relative composition of the diarylnitrone chromophore in these copolymers.

    10. Synthesis of biodegradable copolymers with low-toxicity zirconium compounds. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2-dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high-resolution nuclear magnetic resonance spectroscopy (pages 98–114)

      Piotr Dobrzynski and Janusz Kasperczyk

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21115

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      The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2-dimethyltrimethylene carbonate, conducted in the presence of a low-toxicity zirconium initiator [zirconium(IV) acetylacetonate], are described. The assignment of the spectral NMR lines to appropriate comonomer sequences of copolymeric chains was performed in the methylene proton region of glycolidyl units (1H NMR spectra) and in the carbonyl carbon region (13C NMR spectra).

    11. Phenylglycine derivatives as coinitiators for the radical photopolymerization of acidic aqueous formulations (pages 115–125)

      G. Ullrich, P. Burtscher, U. Salz, N. Moszner and R. Liska

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21139

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      N-Phenylglycine (NPG) was found to be a suitable alternative coinitiator for tertiary amines usually applied with camphorquinone in the polymerization of aqueous acidic formulations. It was demonstrated that the generally poor photoreactivity of aromatic amines had to be assigned to the presence of water and not to the acidity of the formulation. Formulations containing NPGs with electron-withdrawing substituents in R3 showed significantly improved storage stability.

    12. Novel synthesis of N-substituted polyacrylamides: Derivatization of poly(acrylic acid) with amines using a triazine-based condensing reagent (pages 126–136)

      Kimberlee Thompson and Stephen Michielsen

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21042

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      Poly(acrylic acid) (PAA) was derivatized through the reaction of its pendant carboxylic acid (CO2H) groups with a wide range of amine-terminated molecules. These molecules contained alkyl, hydroxyl, sulfonic acid, or perfluoroalkyl groups. N-substitution of PAA was carried out by the simple addition of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM), a triazine-based condensing reagent, to a mixture of PAA and amine-terminated molecules. Functional side-chain contents of greater than 95% were achieved for aqueous reactions with taurine, ethanol amine, and butyl amine, but they were limited to ≤80% for reactions with perfluoroalkyl amines in methanol.

    13. Ring-Opening and polymerization of 1-[2′-(heptaphenylcyclotetrasiloxanyl)ethyl]-1,3,3,5,5-pentamethylcyclotrisiloxane (pages 137–146)

      Thomas M. Gädda and William P. Weber

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21148

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      1-[2′-(Heptaphenylcyclotetrasiloxanyl)ethyl]-1,3,3,5,5-pentamethylcyclotrisiloxane (II) was subjected to acid and base catalyzed ring-opening polymerization. Structures of the monomer and polymers were determined by mass spectrometry, as well as by UV, IR, 1H, 13C, and 29Si NMR spectroscopy. No evidence for ring-opening of the cyclotetrasiloxane ring was observed. Polymer properties were determined by DSC, TGA, and MALDI-TOF.

    14. Formation of elastomeric network polymers from ambient heterogeneous hydrosilations of carboranylenesiloxane and branched siloxane monomers (pages 147–155)

      Manoj K. Kolel-Veetil and Teddy M. Keller

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21151

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      Elastomeric network polymers of carboranylenesiloxanes were synthesized by the ambient heterogeneous Karstedt catalyst catalyzed hydrosilation reactions of a vinyl-terminated carboranylenesiloxane monomer (1) or an ethynyl-terminated carboranylenesiloxane monomer (2) with three-branched siloxane crosslinker monomers [tetrakis(dimethylsiloxyl)silane (4 C-Ls), methyltris(dimethylsiloxyl)silane (3 C-Ls/Me), and phenyltris(dimethylsiloxyl)silane (3 C-Ls/Ph)]. The reactions in hexane were very rapid and produced flexible and transparent films of the network polymers with low glass-transition temperatures in the −60 to 0 °C range depending on the reactants. The high onset temperatures of weight loss of the network polymers bode well for their potential in applications as high-temperature elastomeric materials up to 300 °C.

    15. Interfacial living radical copolymerization of oil- and water-soluble comonomers to form composite polymer capsules (pages 156–171)

      Mir Mukkaram Ali and Harald D. H. Stöver

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21152

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      The suspension copolymerization of methyl methacrylate with hydroxy-functional poly(ethylene glycol) monomethacrylate by atom transfer radical polymerization produced soluble, controlled-molecular-weight amphiphilic copolymers (weight-average molecular weight/number-average molecular weight <1.3). The addition of the optional crosslinker diethylene glycol dimethacrylate resulted in capsule formation.

    16. Synthesis and characterization of poly(fluorene)-based copolymer containing triphenylamine group (pages 172–182)

      Yun-Hi Kim, Qinghua Zhao and Soon-Ki Kwon

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21033

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      The copolymers that are composed of PF, poly(p-phenylene), and Poly(p-phenylenevinylene) as backbone and a large 4′-(N,N′-diphenylamino)diphenyl or 4′-(N,N′-diphenylamino)phenyl as pendent group were synthesized by the nickel(0)-mediated polycoupling. As the content of triphenyl amine pendants increases, the copolymers showed increased thermal stability due to increased glass transition temperature and increased hole injection ability because of decreased onset of the oxidation potential.

    17. Copolymerization of N-vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control (pages 183–191)

      Xingping Qiu and Svetlana A. Sukhishvili

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21153

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      Free-radical copolymerization of N-vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) was investigated to synthesize temperature-responsive reactive copolymers with minimized compositional heterogeneity. Because of very different reactivity ratios for VCL and GMA, VCL–GMA copolymers had highly heterogeneous composition when prepared by batch polymerization. The use of a gradual feeding technique yielded copolymers with much more homogeneous composition, which also showed temperature-triggered phase separation in aqueous solution at temperatures higher than 31 °C. In addition, GMA units in VCL–GMA copolymers were capable of reacting with amino end-functionalized poly(ethylene oxide) at room temperature to produce poly(N-vinylcaprolactam)–poly(ethylene oxide) graft copolymers.

    18. Synthesis and characterization of poly(vinyl amine)-based amphiphilic comb-like dextran glycopolymers by a two-step method (pages 192–199)

      Junmin Zhu, Christine Gosen and Roger E. Marchant

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.20998

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      Amphiphilic comb-like glycopolymers were synthesized using a two-step method involving sequential addition of dextran lactone and N-(hexanoyloxy)succinimide to react with the amine groups on the PVAm backbone. In comparison with the one-step method by simultaneous addition of dextran lactone and alkyl succinimide, the two-step approach can attach Dex on PVAm as high as possible and better control the composition of hydrophilic and hydrophobic chains, which results in better water solubility for the final surfactant polymers.

    19. Ethylene polymerization by novel Ziegler–Natta-type catalysts obtained in situ by the oxidative addition of 8-hydroxyquinoline-based ligands to bis(1,5-cyclooctadiene)nickel(0) and methylaluminoxane (pages 200–206)

      Carlo Carlini, Valentina De Luise, Anna Maria Raspolli Galletti and Glauco Sbrana

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21044

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      Novel catalytic systems, obtained in situ by the oxidative addition of 5-nitro-8-hydroxyquinoline to bis(1,5-cyclooctadiene)nickel(0) [Ni(cod)2] and activated by methylaluminoxane, gave highly linear polyethylene (PE). When the methylaluminoxane cocatalyst was properly formulated, in terms of the free trimethylaluminum content and molar ratio with respect to the transition-metal precursor, an improvement in the PE productivity of more than 1 order of magnitude was achieved [ca. 700 kg of PE/(mol of Ni × h)].

    20. Stimuli-responsive polymers. VIII. Polyesters and poly(ester amides) containing azobenzene and chiral binaphthylene segments: Highly adaptive materials endowed with light-, heat-, and solvent-regulated optical rotatory power (pages 207–218)

      Gary D. Jaycox

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21149

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      Azobenzene-modified polyesters and poly(ester amide)s fitted with chiral, atropisomeric binaphthylene segments were prepared by a series of low-temperature polycondensation reactions. When compared with their polyaramide counterparts studied earlier, these materials had significantly improved solubility behaviors and were readily dissolved by a wide range of organic solvent media. In solution, each of these constructs underwent photoinduced oscillations in optical rotatory power when subjected to multiple UV-light/visible-light illumination cycles that drove trans[LEFT RIGHT ARROW]cis isomerization reactions along their polymer chains. Light-regulated chiroptical perturbations were dependent on polymer backbone structures and were further modulated by well-coordinated temperature fluctuations and by the nature of the solvent medium employed.

    21. Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid (pages 219–225)

      Chen Hou, Rongjun Qu, Chunnuan Ji, Chunhua Wang and Chengguo Wang

      Version of Record online: 10 NOV 2005 | DOI: 10.1002/pola.21174

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      A new catalyst system, FeCl3/isophthalic acid, was successfully used in the reverse atom transfer radical polymerization of acrylonitrile when N,N-dimethylformamide was used as the solvent. The linearity of the plot indicates that the polymerization was approximately first-order with respect to the monomer concentration. The system showed the characteristics of a controlled radical polymerization. An FeCl3-to-isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided a rather rapid reaction rate. Reverse atom transfer radical polymerization was first used to successfully synthesize polyacrylonitrile with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22.

    22. A copper-based reverse atom-transfer radical polymerization process for the living radical polymerization of polyacrylonitrile (pages 226–231)

      Chen Hou, Chunnuan Ji, Chunhua Wang and Rongjun Qu

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21143

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      A new initiator, diethyl 2,3-dicyano-2,3-diphenylsuccinate, was successfully used in the reverse atom-transfer radical polymerization (ATRP) of acrylonitrile in the presence of a catalytic system, CuCl2/2,2′-bipyridine complex. The linearity of this plot indicates that the polymerization is approximately first-order with respect to the monomer concentration. The system shows characteristics of a controlled radical polymerization. CuCl2 to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. Polyacrylonitrile obtained can be used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/biby catalyst system via ATRP process.

    23. Low temperature TEMPO-mediated styrene polymerization in miniemulsion (pages 232–242)

      Michael F. Cunningham, David C. T. Ng, Sarah G. Milton and Barkev Keoshkerian

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21145

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      TEMPO-mediated styrene polymerization was conducted at 100 °C in miniemulsion. Although the traditional operating range of TEMPO is 120–135 °C, we were able to achieve reasonable reaction rates, while preserving a high degree of livingness, through semi-batch addition of ascorbic acid. Polydispersities at higher conversions are ∼1.4–1.6, but chain livingness is comparable with our best experimental results at 135 °C.

    24. Improved EL efficiency of fluorene-thieno[3,2-b]thiophene-based conjugated copolymers with hole-transporting or electron-transporting units in the main chain (pages 243–253)

      Eunhee Lim, Byung-Jun Jung and Hong-Ku Shim

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21144

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      A series of green-light-emitting conjugated copolymers based on fluorene and thieno[3,2-b]thiophene has been synthesized through a palladium-catalyzed Suzuki coupling reaction. New electroluminescent polymers have electron-deficient benzothiadiazole or electron-rich triphenylamine moieties or both in the main chains as third or fourth comonomers. The physical and optical properties of the polymers were carefully characterized. The addition of the benzothiadiazole unit reduced the LUMO energy levels of the polymers, resulting in the increased electron injection. Consequently, EL devices based on the polymers exhibit greater brightness and efficiency than devices that use poly9,9′-dioctylfluorene-co-thieno[3,2-b]thiophene (PFTT).

    25. Synthesis and luminescence characteristics of conjugated dendrimers with 2,4,6-triaryl-1,3,5-triazine periphery (pages 254–263)

      Chae Kyu Kim, Eun Seok Song, Hyung Joo Kim, Chiyoung Park, Young Chul Kim, Jai Kyeong Kim, Jae Woong Yu and Chulhee Kim

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21142

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      We have synthesized conjugated dendrimer with triazine peripheries, and their luminescence properties were investigated. PL study indicates that the energy transfer occurs from the triazine wedges to the stilbene bridge, and finally to the core chromophore units because of a cascade decrease of bandgap from the peripheral wedge to core moiety. With increasing the generation from the first to the second, the energy transfer efficiency decreased due to the increase of distance between the donor and acceptor. The dendrimers have LUMO values of about −2.7 eV and the EL spectra of dendrimers showed emission maximum at 460 nm.

    26. Polymerization of cyclopentadiene initiated by methylaluminoxane (pages 264–272)

      Dongheng Zhang, Wen-Hua Sun, Junxian Hou, Suyun Jie and Fei Chang

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21132

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      The cationic polymerization of cyclopentadiene was effectively initiated by methylaluminoxane. The effects of some reaction parameters on the polymerization were investigated. The kinetics of the polymerization were investigated via gas chromatography. The polymer obtained at a low temperature could be dissolved in toluene or chloroform. 1H NMR and IR analysis of the polymer indicated almost equal amounts of 1,2-enchainment and 1,4-enchainment in the polymer chain.

    27. Acrylic polymer/silica hybrids prepared by emulsifier-free emulsion polymerization and the sol–gel process (pages 273–280)

      Toshiyuki Tamai and Mitsuru Watanabe

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21155

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      Acrylic polymer/silica hybrid films prepared from emulsifier-free acrylic polymer emulsions 13 and tetraethoxysilane (TEOS) were transparent and solvent-resistant. Atomic force microscopy studies of the hybrid film surface suggested that the silica component was dispersed homogeneously in the acrylic polymer component. The Si[BOND]O[BOND]Si bond formed by the cocondensation of TEOS and triethoxysilyl groups on the acrylic polymers played an important role in the homogeneous dispersion of the silica component.

    28. Intricate relation between the content and interactive roles of β-cyclodextrin in fixing the characteristics of conducting polyaniline composites (pages 281–294)

      G. Anitha and E. Subramanian

      Version of Record online: 11 NOV 2005 | DOI: 10.1002/pola.21133

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      β-Cyclodextrin (CD) in polyaniline (PANI) composites has two roles, dopant and encapsule. CD lies between two adjacent PANI chains and, together with included SOmath image ions, acts as a dopant. Also, it includes part of the PANI chain randomly with phenyl in a flat configuration and functions as an encapsule. The content of CD in these two roles, which varies with the experimental conditions, has a contrasting influence on the characteristics of PANI in composites. This ultimately leads to an intricate relation between the interactive roles of CD and its total content.

    29. Syntheses of cyclodextrin–3′-azido-3′-deoxythymidine conjugates and their sulfates with improved anti-HIV activities (pages 295–303)

      Ildoo Chung, Chong-Kyo Lee, Chang-Sik Ha and Won-Jei Cho

      Version of Record online: 14 NOV 2005 | DOI: 10.1002/pola.21101

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      New anti-HIV agents, cyclodextrin–succinate diester–3′-azido-3′-deoxythymidine (CD–AZT) conjugates, were synthesized by molecular design and characterized. Their sulfates were prepared by the reaction of CD–AZT conjugates with a sulfur trioxide/pyridine complex. The in vitro antiviral activities of the conjugates and their sulfates [sulfated cyclodextrin–succinate diester–3′-azido-3′-deoxythymidine (SCD–AZT)] were determined to evaluate the potential applications in anti-HIV drugs. In vitro anti-HIV activities indicated that the synthesized conjugates and their sulfates (SCD–AZT) against HIV-1 and HIV-2 strains were much better inhibitors than 3′-azido-3′-deoxythymidine.

    30. Mono-, bis-, and trismaleimides having electron-donating chromophores: Fluorescence, electrochemical properties, polymerization, and cure monitoring (pages 304–313)

      Xin Zhang, Zi-Chen Li, Zhe-Ming Wang, Hao-Ling Sun, Zheng He, Kai-Bo Li, Liu-He Wei, Song Lin, Fu-Sheng Du and Fu-Mian Li

      Version of Record online: 14 NOV 2005 | DOI: 10.1002/pola.21113

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      Mono-, bis-, and trismaleimides having electron-donating chromophores displayed fluorescence quenching due to an intramolecular charge-transfer interaction. Electrochemistry studies revealed their intramolecular quenching mechanism. On the basis of the electrochemical data, an energy level diagram was established for these maleimides. In a novel trismaleimide resin, TM-6 was a dual-purpose functional monomer, which acted not only as a crosslinker but also as an intrinsic fluorophore to monitor its cure process.

    31. Investigations of the dissociation behavior and interfacial adsorption characteristics of polyelectrolytes from poly(acrylamido-2-methyl-1-propane sulfonic acid) with an octadecyl side chain (pages 314–324)

      K. Chandrasekar and Geetha Baskar

      Version of Record online: 14 NOV 2005 | DOI: 10.1002/pola.21075

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      Acrylamido-2-methyl-1-propane sulfonic acid (AMPS)-derived copolymers with octadecyl chains exhibit dissociation behavior governed by solution structures. The destabilization effect on the sulfate anion upon neutralization due to electrostatic repulsion affects the dissociation characteristics of these polymers. A continuous expansion of the coil upon neutralization is preferred to overcome these effects, and this is indicated by a high pK value. The copolymers, acrylamido-2-methyl-1-propane sulfonic acid/octadecyl maleamic acid and acrylamido-2-methyl propane sulfonic acid/octadecyl maleate ester, exhibit organization at the air/solution interface, exhibiting an expanded conformation, as suggested from the surface area of 78 ± 3.5 Å2/molecule.

    32. Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate (pages 325–334)

      Ryosuke Sakai, Issei Otsuka, Toshifumi Satoh, Ryohei Kakuchi, Harumi Kaga and Toyoji Kakuchi

      Version of Record online: 14 NOV 2005 | DOI: 10.1002/pola.21074

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      The asymmetric polymerization of 4′-isocyanatobenzo-18-crown-6 with the lithium amide of (S)-(2-methoxymethyl)pyrrolidine successfully proceeded to afford end-functionalized poly(4′-isocyanatobenzo-18-crown-6) with (S)-(2-methoxymethyl)pyrrolidine (polymer 2). From the circular dichroism measurements of 2, it was found that the extremely stable, one-handed helical part should exist in the main chain of 2. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests, whose driving force should certainly be attributed to the one-handed helical structure in 2.

    33. Characterization and corrosion resistance of organically modified silicate/MO2 (M = Zr, Ti, or Ce) hybrid coatings on a 6061-T6 aluminum alloy (pages 335–342)

      K. H. Wu, M. C. Li, T. C. Chang and C. C. Yang

      Version of Record online: 14 NOV 2005 | DOI: 10.1002/pola.21094

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      Hybrid coatings based on organically modified silicates (Ormosil)/ZrO2 (0–1.0 wt %) and Ormosil/MO2 (M = Ti or Ce) were synthesized through a sol–gel technique. These hybrid films were deposited via spin coating onto an aluminum alloy to improve the corrosion protection. The effects of the ZrO2 content and the metallic particles (ZrO2, TiO2, and CeO2) on the chain dynamics, thermal stability, and corrosion resistance were characterized by nuclear magnetic resonance, thermogravimetric analysis, and electrochemical measurements. The results of the nuclear magnetic resonance and potentiodynamic polarization curve analysis provided evidence that the Ormosil hybrids had a denser configuration when metallic particles were incorporated and then prevented the corrosion of the aluminum alloy substrate.

    34. Synthesis and polymerization reactions of cyclic imino ethers. I. Ring-opening homopolyaddition of AB-type hydroxyphenyl-substituted 2-oxazolines (pages 343–355)

      Jozef Lustoň, Juraj Kronek and Frank Böhme

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21159

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      We propose a mechanism that involves a polymer growth reaction and a side reaction that leads to branching. According to part A of the scheme and in agreement with Mülhaupt, the main reaction proceeds by a thermally initiated nucleophilic attack of the phenolic group to the methylene group in position 5 of the 2-oxazoline ring, without the formation of ionic structures. In fact, the reaction is the AN2 type. With progressive conversion, the abundance of reactive phenol groups in the vicinity of oxazoline groups decreases, whereas the number of amidic groups increases. This makes the side reaction, as shown in part B, more likely. The side reaction proceeds with the AN2 mechanism (part B).

    35. Preparation, morphology, and thermoresponsive properties of poly(N-isopropylacrylamide)-based copolymer microgels (pages 356–370)

      Chia-Lung Lin, Wen-Yen Chiu and Chia-Fen Lee

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21134

      Thumbnail image of graphical abstract

      Thermoresponsive copolymer latex particles with an average diameter of about 200–500 nm were prepared via surfactant-free emulsion polymerization. The thermoresponsive properties of these particles were designed by the addition of hydrophilic monomers (acrylic acid and sodium acrylate) to copolymerize with N-isopropylacrylamide. The effects of the comonomers and composition on the synthesis mechanism, kinetics, particle size, morphology, and thermoresponsive properties of the copolymer latex were also studied to determine the relationship between the synthesis conditions, the particle morphology, and the thermoresponsive properties. It was concluded that these submicrometer copolymer latex particles with different thermoresponsive properties could be applied in many fields.

    36. Isoconversional method to explore the cure reaction mechanisms and curing kinetics of DGEBA/EMI-2,4/nano-SiC system (pages 371–379)

      Tianle Zhou, Mingyuan Gu, Yanping Jin and Junxiang Wang

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21150

      Thumbnail image of graphical abstract

      The curing kinetics of the diglycidyl ether of bisphenol-A (DGEBA)/2-ethyl-4-methylimidazole (EMI-2,4)/nano-sized carborundum (nano-SiC) system was studied by means of nonisothermal differential scanning calorimetry (DSC). An isoconversional method of kinetic analysis yields a dependence of the effective activation energy E on the extent of conversion that decreases initially, and then increases as the cure reaction proceeds. The variations of E were used to study the cure reaction mechanisms, and the Shrinking Core Model was used to study the resin–particle reaction. The results show that the presence of nano-SiC particles prevents from the occurrence of vitrification, as well as inhibiting the cure reaction.

    37. “One-pot” synthesis of aromatic poly(1,3,4-oxadiazole)s in novel solvents—ionic liquids (pages 380–394)

      Elena I. Lozinskaya, Alexander S. Shaplov, Mariya V. Kotseruba, Lidiya I. Komarova, Konstantin A. Lyssenko, Mikhail Y. Antipin, Denis G. Golovanov and Yakov S. Vygodskii

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21141

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      The new convenient method for the synthesis of high molecular weight aromatic poly(1,3,4-oxadiazole)s (PODs) has been proposed. These polymers were prepared by “one–pot” procedure from dicarboxylic acid and hydrazine's salt (sulfate, phosphate) or dicarboxylic acid dihydrazides. The mixture of ionic liquid and triphenyl phosphite was used both as a solvent and condensing agent. The polycyclization occurred at a sufficiently low temperature of 210 °C for 2–5 h and resulted in obtaining film-forming PODs having inherent viscosities up to 0.9 dL/g and good thermal stability.

    38. Detailed study of the ring-opening metathesis polymerization of norbornene bearing a five- or six-membered ring cyclic carbonate along with volume expansion (pages 395–405)

      Tetsuo Hino, Naoto Inoue and Takeshi Endo

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21073

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      The specific ring-opening metathesis polymerization (ROMP) behavior of norbornene derivative bearing 6- or 5-membered cyclic carbonate along with volume expansion was investigated by using typical Grubbs catalyst, where the polymerizations proceeded along with volume expansion. Additionally, the degree of volume change was found to be influenced at least by the Mn, Tg and the proportion of cis or trans/configuration of the exocyclic double bonds of the resulting polymer. The Sc(OTf)3 mediated cationic ring-opening reaction of the cyclic carbonate moiety of the resulting polyalkenamers was efficiently carried out to give the corresponding networked polymers with the volume expansion or nearly zero volume shrinkage.

    39. Synthesis of unimolecular reversed micelle consisting of a poly(L-lactide) shell and hyperbranched D-mannan core (pages 406–413)

      Toshifumi Satoh, Masaki Tamaki, Yoshikazu Kitajyo, Takahiro Maeda, Hiroyuki Ishihara, Tomoko Imai, Harumi Kaga and Toyoji Kakuchi

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21171

      Thumbnail image of graphical abstract

      A novel biodegradable unimolecular reversed micelle consisting of a poly(L-lactide) (PLA) shell and a hyperbranched D-mannan (HBM) core, that is, a chestnut-shaped polymer (PLA–HBM), was synthesized by the polymerization of the L-lactide on HBM with 4-(dimethylamino)pyridine as the catalyst. The obtained copolymer, PLA–HBM, acted as a unimolecular reversed micelle with an encapsulation ability toward the hydrophilic molecule. In addition, the entrapped hydrophilic molecules were slowly released from the core of PLA–HBM, and the release rate was accelerated by the breaking of the PLA chains of the shell when proteinase K as a hydrolase of PLA was used. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    40. Nitroxide-mediated radical polymerization of 2-(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N-butyl acrylate (pages 414–426)

      Kejian Bian and Michael F. Cunningham

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21147

      Thumbnail image of graphical abstract

      Nitroxide-mediated radical polymerization (NMRP) of 2-(dimethylamino)ethyl acrylate (DMAEA) was carried out in bulk and in organic solvents at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethylpropyl)nitroxide, SG1. In the presence of additional SG1, polymerizations remain controlled, with kinetic plots linear within 55–70% conversion. The molecular weights are proportional with conversions, though deviating to some extent with theoretical values. From poly(styrene) and poly(n-butyl acrylate) macroinitiators, a series of block copolymers containing different length of DMAEA segments were synthesized via NMRP.

    41. Comparative study of classical surfactants and polymerizable surfactants (surfmers) in the reversible addition–fragmentation chain transfer mediated miniemulsion polymerization of styrene and methyl methacrylate (pages 427–442)

      H. Matahwa, J. B. McLeary and R. D. Sanderson

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21071

      Thumbnail image of graphical abstract

      The reversible addition–fragmentation chain transfer process was used in miniemulsion polymerization reactions stabilized by cationic and anionic amphiphilic monomers (surfmers) to control the molecular weight distributions. The reaction rates of the surfmer-stabilized miniemulsion polymerization of styrene and methyl methacrylate were similar (in most cases) to those of the classical-surfactant-stabilized miniemulsion polymerizations. The final particle sizes were also similar for polystyrene latexes stabilized by the surfmers and classical surfactants. However, poly(methyl methacrylate) latexes stabilized by the surfmers had larger particle sizes than latexes stabilized by classical surfactants.

    42. Synthesis and characterization of saccharide-based latex particles (pages 443–457)

      Ainara Imaz, Mirari Ayerbe, Jose Ramos and Jacqueline Forcada

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21157

      Thumbnail image of graphical abstract

      The synthesis of new polymer colloids based on renewable resources, such as sugar-derived monomers, is nowadays a matter of interest. These new polymeric particles should be useful in biomedical applications, such as drug delivery, because of their assumed biodegradability. In this work, two new families of polymer latex particles based on a sugar-derived monomer, 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (3-MDG), were produced and characterized. The syntheses of poly(3-MDG) crosslinked particles and those obtained by copolymerization with methacrylic acid (MAA), poly(3-MDG-co-MAA) crosslinked particles, were prepared by surfactant-free emulsion polymerization in a batch reactor. Poly(3-MDG-co-EGDMA) stable particles were obtained by adding low amounts of initiator. The surface-charge density of these particles corresponded to the sulfate groups coming from the initiator. In the second family of latices, poly(3-MDG-co-MAA-co-EGDMA) particles, DCP measurements and SEM and TEM observations showed that the sizes and surface characteristics depended on the amounts of MAA and crosslinker used in the reaction mixture.

    43. Propylene polymerization with nickel–diimine complexes containing pseudohalides (pages 458–466)

      Marcos L. Dias, Luciana P. da Silva, Geraldo L. Crossetti, Griselda B. Galland, Carlos A. L. Filgueiras and Cláudio M. Ziglio

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21013

      Thumbnail image of graphical abstract

      New DADNiX2 nickel–diimine complexes [DAD = 2,6-iPr2[BOND]C6H3[BOND]N[DOUBLE BOND]C(Me)[BOND]C(Me)[DOUBLE BOND]N[BOND]2,6-iPr2[BOND]C6H3] containing nonchelating pseudohalide ligands (X = isothiocyanate or isoselenocyanate) were prepared and applied to propylene polymerization with methylaluminoxane (MAO) and were compared with a known Br analogue. These catalyst systems produced high-molecular-weight amorphous propylene polymers with structures similar to those of propylene–ethylene copolymers containing moderately syndiotactic propylene sequences and ethylene sequences.

    44. Synthesis and characterization of amphiphilic copolymer of linear poly(ethylene oxide) linked with [poly(styrene-co-2-hydroxyethyl methacrylate)-graft-poly(ε-caprolactone)] using sequential controlled polymerization (pages 467–476)

      Xuewei Xu and Junlian Huang

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21162

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      By combining reversible addition-fragmentation chain transfer polymerization (RAFT) with coordination-insertion ring-opening polymerization (ROP), a new copolymer PEO-b-[P(St-co-HEMA)-g-PCL] was successfully prepared. The coupling of mPEO with ω,3-benzylsulfanylthiocarbonylsufanylpropionic acid (BSPA) was conducted first, the efficiency was nearly 100%. Then the copolymerization of St and HEMA was carried out in the presence of macro-RAFT agent mPEO-BSPA and finally the ε-caprolactone was polymerized by initiation of hydroxyl groups of HEMA units of the copolymer, the object copolymer of PEO-b-[P(St-co-HEMA)-g-PCL] was obtained.

    45. New method of synthesis of electroactive polyamide with amine-capped aniline pentamer in the main chain (pages 477–482)

      Danming Chao, Xiaofeng Lu, Jingyu Chen, Xiaogang Zhao, Lifeng Wang, Wanjin Zhang and Yen Wei

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21158

      Thumbnail image of graphical abstract

      Well-defined molecular structure electroactive polyamide with amine-capped aniline pentamer in the main chain was prepared by a novel approach of oxidative coupling polymerization of the derivative of oligoaniline and p-phenylenediamine. Neither the synthesis of the amine-capped aniline pentamer nor the protection of the secondary amino group of oligoaniline is needed in this method. Furthermore, the size, structure, and properties of the resultant product were characterized by FTIR, 1H NMR, EA, GPC, UV-vis spectra, cyclic voltammetry (CV), thermogravimetric analysis (TGA), and electrical conductivity measurement.

    46. Iron-mediated atom transfer radical polymerization of styrene with tris(3,6-dioxaheptyl) amine as a ligand (pages 483–489)

      Gang Wang, Xinlin Zhu, Jian Zhu and Zhenping Cheng

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21172

      Thumbnail image of graphical abstract

      Tris(3,6-dioxaheptyl) amine was used as a ligand for the heterogeneous iron-mediated atom transfer radical polymerization of styrene. The rates of polymerizations exhibited first-order kinetics with respect to the monomer, and a linear increase in the predicted number-average molecular weight with increasing monomer conversion was observed for this catalytic system. Because of its water solubility, the iron complexes could be removed easily from the reaction mixture through the washing of the polymerization mixture with water.

    47. Dibenzyl trithiocarbonate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile (pages 490–498)

      Xiao-Hui Liu, Gui-Bao Zhang, Xian-Feng Lu, Jing-Yu Liu, Ding Pan and Yue-Sheng Li

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21169

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      Well-defined polyacrylonitrile with a narrow polydispersity was synthesized by the reversible addition–fragmentation chain transfer polymerization technique with dibenzyl trithiocarbonate as the chain-transfer agent. The polymerizations displayed living/controlled free-radical polymerization characteristics, as evidenced by the narrow polydispersity, pseudo-first-order kinetics of polymerization, controlled molecular weight, linear evolution of the molecular weight with increasing monomer conversion, and constant concentration of active centers during the polymerization. The key to success was ascribed to the improvement of the interchange frequency between dormant and active species. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and 1H NMR as well as the chain-extension reaction confirmed the very high chain-end functionality of the polyacrylonitrile obtained.

    48. Preparation of ABC miktoarm star terpolymer containing poly(ethylene glycol), polystyrene, and poly(tert-butylacrylate) arms by combining diels–alder reaction, atom transfer radical, and stable free radical polymerization routes (pages 499–509)

      Hakan Durmaz, Figen Karatas, Umit Tunca and Gurkan Hizal

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21160

      Thumbnail image of graphical abstract

      The ABC type miktoarm star terpolymer was prepared utilizing “core-in” and “core-out” methods via combination of Diels–Alder reaction (DA), stable free radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). The miktofunctional initiator (11) was used as core. The resultant ABC type miktoarm star terpolymer (11) with low polydispersity (Mw/Mn < 1.27) contains poly(ethylene glycol) (PEG), polystyrene (PSt), and poly(tert-butylacrylate) (PtBA) arms.

    49. Synthesis of well-defined naphthalene and photo-labile group-labeled polystyrene via ATRP (pages 510–518)

      Wei Zhang, Nianchen Zhou, Jian Zhu, Bin Sun and Xiulin Zhu

      Version of Record online: 15 NOV 2005 | DOI: 10.1002/pola.21166

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      A novel photoiniferter reagent, (1-naphthyl)methyl N,N-diethyldithiocarbamate (NMDC), was successfully introduced into atom transfer radical polymerization of styrene (St) in the presence of copper (I) bromide (CuBr) and N,N,N′,N″,N″-pentamethyldiethylenetriamine. The results showed that NMDC was an effective initiator with high initiation efficiency for ATRP of St. The polymerization rate was first-order with respect to the monomer concentration, and the molecular weights of the obtained polystyrene increased linearly with the monomer conversions, with very narrow molecular weight distributions (Mw/Mn = 1.07–1.29).

    50. Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups (pages 519–531)

      Chun-Hao Huang, Sheng-Hsiung Yang, Kuei-Bai Chen and Chain-Shu Hsu

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21163

      Thumbnail image of graphical abstract

      Five novel fluorine-containing polyacetylenes (PFA1–PFA5) were synthesized and characterized. The PL spectra of PFAs in the solution show from blue to yellow emissions. Emission properties of these polyacetylenes were improved with double layer devices of the type ITO/PEDOT/PFAS/Ca/Al. The turn-on voltage of a PFA5-fabricated device was 2.8 V, and a maximum brightness of 923 cd/m2 could be observed at 8 V. This is the brightness polyacetylene red EL device to date.

    51. New solvent for polyrotaxane. I. Dimethylacetamide/lithium chloride (DMAc/LiCl) system for modification of polyrotaxane (pages 532–538)

      Jun Araki and Kohzo Ito

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21179

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      A polyrotaxane consist of α-CD and PEG was found to be dissolved in a solvent system of dimethylacetamide (DMAc) containing 8–9% of lithium salt. The polyrotaxane solution thus obtained was useful for various modifications of polyrotaxane, which were unsuccessful in the previous solvents of polyrotaxane, i.e. DMSO and aqueous NaOH. Preparations of polyrotaxane acetate and dansylate were investigated further in detail, and compared with the reactions in DMSO.

    52. A new synthetic route to borane-terminated isotactic polypropylenes via styrene/hydrogen consecutive chain transfer reaction (pages 539–548)

      Guoqiang Fan, Jin-Yong Dong, Zhigang Wang and T. C. Chung

      Version of Record online: 18 NOV 2005 | DOI: 10.1002/pola.21180

      Thumbnail image of graphical abstract

      The consecutive chain transfer reaction, first to a trialkylborane-containing styrene derivative, 4-[B-(n-butylene)-9-BBN] styrene (B-styrene), then to hydrogen in propylene polymerization catalyzed by rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MAO resulted in borane-terminated i-PP that kept the desired properties of a polymeric alkyl-9-BBN reagent. This new process of preparing borane-terminated polyolefin avoided the use of B-H-containing chain transfer agent and could be carried out with Al-activated metallocene catalyst under mild reaction conditions.

    53. Synthesis and characterizations of well-defined branched polymers with AB2 branches by combination of RAFT polymerization and ROP as well as ATRP (pages 549–560)

      Bin Luan, Bao-Qing Zhang and Cai-Yuan Pan

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21183

      Thumbnail image of graphical abstract

      A synthetic strategy of well-defined branched copolymers with AB2 branches using “graft from” method has been developed successfully. The side group CH2OH in the poly (methyl acrylate-co-(2-hydroxyethyl) acrylate) (poly(MA-co-HEA)) main chain displayed high initiation efficiency in the ring-opening polymerization of LLA. After the divergent reaction of the product obtained with 2,2-bis(methylene α-bromoisobutyrate)propionyl chloride (BMBIBPC), and the poly(MA-co-HEA)-g-PLLABr2 was used in the successive atom transfer radical polymerization of styrene, the branched copolymers having the PLLA-b-PS2 branches with controlled branch number, molecular weight and narrow molecular weight distribution were obtained.

    54. Anionic polymerization of 2,7-di-t-butyldibenzofulvene: Synthesis, structure, and photophysical properties of the oligomers with a π-stacked conformation (pages 561–572)

      Tohru Yade and Tamaki Nakano

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21164

      Thumbnail image of graphical abstract

      2,7-Di-t-butyldibenzofulvene (tBu2DBF) afforded mainly oligomers up to trimer in addition to a small amount of polymer by anionic polymerization. In the trimer conformation, the fluorene moieties of the central and the initiation-side monomeric units were found to be stacked on top of each other, while the termination-side monomeric unit appeared to be in a faster conformational dynamics. The trimer indicated hypochromicity in absorption spectra but no clear excimer emission in fluorescent spectra, indicating that the two stacked fluorene moieties are unable to form a very close stack suitable for excimer formation on photo excitation because of steric effects of t-butyl groups.

    55. Singlewall carbon nanotubes covered with polystyrene nanoparticles by in-situ miniemulsion polymerization (pages 573–584)

      Hyeong Taek Ham, Yeong Suk Choi, Mu Guen Chee and In Jae Chung

      Version of Record online: 16 NOV 2005 | DOI: 10.1002/pola.21185

      Thumbnail image of graphical abstract

      Singlewall carbon nanotubes covered with polystyrene nanoparticles were prepared via in-situ miniemulsion polymerization. Polystyrene nanoparticles were attached on the surface of singlewall carbon nanotubes. The nanoparticles partially covered the sidewall of carbon nanotubes. The bare surface of singlewall carbon nanotubes and polystyrene nanoparticle attached singlewall carbon nanotubes were coexisted. Polystyrene-singlewall carbon nanotube composites were prepared with three different methods: miniemulsion polymerization, conventional emulsion polymerization, and mixing SWNT with PS latex. Their structural difference and properties were examined.

    56. Precise synthesis of porphyrin array scaffolding polyisocyanides (pages 585–595)

      Fumie Takei, Daisuke Kodama, Sugiko Nakamura, Kiyotaka Onitsuka and Shigetoshi Takahashi

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/pola.21186

      Thumbnail image of graphical abstract

      Aryl isocyanides bearing free-base and metallo-porphyrins were prepared and polymerized with a Pd–Pt μ-ethynediyl complex as the initiator to give polymers with narrow polydispersity indexes. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo-porphyrin polymers were also prepared by reacting free-base porphyrin polymers with metal salts.

    57. Versatile and controlled synthesis of resorbable star-shaped polymers using a spirocyclic tin initiator—Reaction optimization and kinetics (pages 596–605)

      Karin Odelius, Anna Finne and Ann-Christine Albertsson

      Version of Record online: 17 NOV 2005 | DOI: 10.1002/pola.21192

      Thumbnail image of graphical abstract

      Well defined star-shaped polyesters were synthesized using a spirocyclic tin initiator, where L-lactide was chosen as a model system for the investigation of the polymerization kinetics. Dichloromethane, chloroform, toluene, and chlorobenzene were chosen as the solvents and used just below their boiling point and when possible also at 40, 60, 80, and 110 °C. It is concluded that neither the temperature nor the solvent affects the molecular weight or the molecular-weight distribution of the star-shaped polymers, which all show a molecular-weight distribution below 1.19 and a molecular weight determined by the initial monomer to initiator concentration.

    58. Double hydrophilic block copolymers of sodium(2-sulfamate-3-carboxylate)isoprene and ethylene oxide (pages 606–613)

      Stergios Pispas

      Version of Record online: 17 NOV 2005 | DOI: 10.1002/pola.21196

      Thumbnail image of graphical abstract

      Poly(sodium(2-sulfamate-3-carboxylate)isoprene)-b-poly (ethylene oxide) and poly(ethylene oxide)-b-poly(sodium(2-sulfamate-1-carboxylate)isoprene)-b-poly(ethylene oxide) double hydrophilic block copolymers were prepared by selective post polymerization reaction of the polyisoprene block, of poly(isoprene-b-ethylene oxide) diblocks or poly(ethylene oxide-b-isoprene-b-ethylene oxide) triblock precursors synthesized by anionic polymerization high vacuum techniques, with N-chlorosulfonyl isocyanate. Viscometry and dynamic light scattering revealed a complex dilute solution behavior of the novel block copolymers, resulting from the polyelectrolyte character of the functionalized PI block and showing a dependence on solution ionic strength and pH.

    59. Synthesis and characterization of model 3-miktoarm star copolymers of poly(dimethylsiloxane) and poly(2-vinylpyridine) (pages 614–619)

      Panagiota G. Fragouli, Hermis Iatrou, Nikos Hadjichristidis, Takuro Sakurai and Akira Hirao

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/pola.21197

      Thumbnail image of graphical abstract

      Well-defined 3-miktoarm star copolymers, with two poly(dimethylsiloxane) (PDMS) and one poly(2-vinylpyridine) (P2VP) arm, were synthesized by using anionic polymerization–high vacuum techniques and (chloromethylphenylethyl)methyl dichlorosilane, heterofunctional linking agent, with two SiCl groups and one CH2Cl group. The synthesis was based on the selective reaction of the two [BOND]SiCl groups with PDMSOLi living chains, followed by reaction of the remaining chloromethyl group with P2VPLi.

    60. Homo- and copolymerization of methyl methacrylate with ethylene by novel Ziegler-Natta-Type nickel catalysts based on N,O-nitro-substituted chelate ligands (pages 620–633)

      Carlo Carlini, Valentina De Luise, Marco Martinelli, Anna Maria Raspolli Galletti and Glauco Sbrana

      Version of Record online: 17 NOV 2005 | DOI: 10.1002/pola.21161

      Thumbnail image of graphical abstract

      The homopolymerization of methyl methacrylate (MMA) and its copolymerization with ethylene have been studied in the presence of new Ni(II) catalytic systems based on N,O chelate ligands, activated by methylaluminoxane. The obtained poly(methyl methacrylate)s display a prevailing syndiotacticity, high molecular weight, and large polydispersity. The copolymerization products are characterized by highly linear polyethylenes containing 1,5-2 mol % of MMA counits, for potential application as materials with improved surface properties.

    61. Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources (pages 634–645)

      G. Lligadas, J. C. Ronda, M. Galià, U. Biermann and J. O. Metzger

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/pola.21201

      Thumbnail image of graphical abstract

      Oligomeric polyether polyols were obtained through the acid-catalyzed ring-opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′-methylenebis(phenyl isocyanate) to yield polyurethanes, which could behave as hard rubbers or rigid plastics.

    62. Synthesis and interfacial behaviors of amphiphilic poly(oxypropylene) amidoacids (pages 646–652)

      Kuan-Liang Wei, Fei-Yu Hung and Jiang-Jen Lin

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21202

      Thumbnail image of graphical abstract

      A series of hydrophobic poly(oxypropylene) (POP)-backboned and hydrophilic poly(oxyethylene)-backboned amidoacids and imidoacids were prepared through the reaction of poly-(oxyalkylene) diamines and trimellitic anhydride (TMA) under mild conditions. The synthesized copolymers were characterized with nuclear magnetic resonance and Fourier transform infrared. Their ability to lower the water surface tension and toluene/water interfacial tension was measured and correlated with the hydrophobic/hydrophilic balance with multiple sodium carboxylate functionalities. The specific POP2000/TMA copolymers, consisting of a 2000 g/mol POP segment and multiple amidoacid functionalities, enabled the demonstration of a strong surfactant tendency and a critical micelle concentration at 0.1 wt %.

  3. Rapid Communications

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communications
    5. Note
    6. Notes
    1. Fabrication of a pore-connected, macroporous, crosslinked polystyrene monolith with anhydride groups bonded onto a pore surface (pages 653–658)

      Jin-Wei Fan, Jian-Yuan Deng, Chang-Min Xing and Wan-Tai Yang

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21146

      Thumbnail image of graphical abstract

      A schematic diagram is shown for fabricating macroporous, crosslinked polystyrene monoliths.

    2. Controlled nitroxide-mediated and reversible addition–fragmentation chain transfer polymerization of N-vinylpyrrolidone: Synthesis of block copolymers with styrene and 2-vinylpyridine (pages 659–665)

      Panayiotis Bilalis, Marinos Pitsikalis and Nikos Hadjichristidis

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21198

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      Nitroxide-mediated polymerization (NMP) and reversible addition–fragmentation chain transfer (RAFT) polymerization were applied to the controlled polymerization of N-vinylpyrrolidone. In the case of NMP, 2,2,6,6-tetramethyl-1-(phenylethoxy)piperidine and 2,2,6,6-tetramethylpiperidinyloxy radical (TEMPO) were employed as unimolecular and bimolecular initiating systems, respectively. Three different chain-transfer agents were used under various experimental conditions for the RAFT polymerization methodology. The controlled/living character of the poly(N-vinylpyrrolidone) homopolymers was confirmed by the successful synthesis of block copolymers with styrene and 2-vinylpyridine.

    3. Metal-ion-mediated healing of gels (pages 666–670)

      Shyni Varghese, Ashish Lele and Raghunath Mashelkar

      Version of Record online: 28 NOV 2005 | DOI: 10.1002/pola.21177

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      Several researchers have demonstrated the biomimicking attributes of stimuli responsive synthetic hydrogels such as sensitivity, selectivity, mobility, and memory. In this work we demonstrate yet another attribute, namely healing in hydrogels. We show that certain hydrogels having a flexible aliphatic side chain with a terminal carboxyl group can show healing in the presence of transition metal ions. On bringing two initially dried gel pieces into contact with each other in a dilute copper chloride solution the pieces were found to weld and the strength of the weld-line was found to increase gradually with time. The welded gel pieces could be separated by leaching out the metal ions and the separated gel pieces can be welded again by subsequent treatment with the metal ions.

    4. Injectable thermoreversible hydrogels based on amphiphilic poly(amino acid)s (pages 671–675)

      Yasushi Takeuchi, Hiroshi Uyama, Naoki Tomoshige, Eiji Watanabe, Yoichi Tachibana and Shiro Kobayashi

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21189

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      Injectable thermoreversible poly(amino acid) hydrogels have been developed. Amphiphilic poly(α/β-asparagine) derivatives, synthesized by the reaction of polysuccinimide with a combination of hydrophilic and hydrophobic amines, showed a sharp sol–gel–sol transition in an aqueous solution. The transition temperature could be controlled by the side-chain structure of the poly(amino acid)s.

    5. Cp*RuCl(η2-CH2[DOUBLE BOND]CHCN)(PPh3): A novel catalyst for atom transfer radical polymerization of styrene and the effect of Et2NH as additive (pages 676–680)

      Aidé Saenz-Galindo, Hortencia Maldonado Textle, Alfredo Rosales Jasso and José Román Torres-Lubián

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21182

      Thumbnail image of graphical abstract

      The well-defined organometallic compound Cp*RuCl(η2-CH2 [DOUBLE BOND]CHCN)(PPh3) in conjunction with ethyl 2-bromopropionate as initiator promote controlled/living radical polymerization of styrene at 90°C. Molecular weight increased linearly with conversion and was in good agreement with the theoretical molecular weight. Observed polydispersities were narrow (1.07–1.04) and decreased with monomer conversion. When a proportion of 5:1 equivalents of diethylamine:initiator was added to the initiating system, an increase of 9 times in the polymerization rate was observed, keeping a good control of polymerization process, as polydispersity changed to 1.09–1.17.

  4. Note

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communications
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      Unexpected substituent effect by a comonomer unit on the reactivity of an isocyanate group in a copolymer side chain (pages 681–685)

      Yoshiteru Itagaki, Atsushi Sudo and Takeshi Endo

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.21127

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      The reactivity of an isocyanate group in a polymethacrylate side chain with benzyl alcohol was examined. The introduction of a long, linear alkyl chain such as a butyl or lauryl group into the side chain of the polymer led to unexpected acceleration of the reaction in its early stage, and this suggested a tendency of the linear alkyl chain to self-organize and thus thrust the polar isocyanate group into its microdomain with a locally high concentration of the isocyanate group.

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      Structure–property relationship in chitosan-based biopolymer/montmorillonite nanocomposites (pages 686–696)

      Shaofeng Wang, Ling Chen and Yuejin Tong

      Version of Record online: 21 NOV 2005 | DOI: 10.1002/pola.20941

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      Three kinds of chitosan-based biopolymer/montmorillonite (MMT) nanocomposites have been prepared by an exfoliation–adsorption method. The structure of MMT is tailored by the functional groups of the polymer matrix. Chitosan/MMT nanocomposites form intercalated-and-flocculated structures, whereas with the introduction of carboxymethyl into chitosan, N,O-carboxymethyl chitosan/MMT nanocomposites form even stronger flocculated structures. On the other hand, direct quaternization of the amino group of chitosan to form N,N,N-trimethyl chitosan chloride/MMT nanocomposites gives a nearly exfoliated structure. The nanodispersion of MMT in the biopolymer matrices affects the thermal degradation mechanism in different ways corresponding to the different kinds of functional groups that are introduced into the chitosan matrix.

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