Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 42 Issue 19

1 October 2004

Volume 42, Issue 19

Pages 4723–5030

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. You have free access to this content
      Biodegradable polymers with variable architectures via ring-expansion polymerization (pages 4723–4742)

      Hans R. Kricheldorf

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20261

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      Various cyclic and spirocyclic 1,3-dioxa-2-metalla compounds were prepared and used as initiators for the ring-expansion polymerization of lactones, lactides, and cyclocarbonates. In situ combinations with numerous (poly)condensation reactions yielded a broad variety of biodegradable materials with functional groups and variable architectures.

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      Fundamental kinetic aspects of living radical polymerization and the use of gel permeation chromatography to shed light on them (pages 4743–4755)

      Takeshi Fukuda

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20325

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      The control achievable by living radical polymerization (LRP) is based on a kinetic balance of the activation–deactivation reversible reactions with conventional elementary reactions. This work explains how chains grow and how their polydispersity evolves as they experience activation–deactivation cycles and how these processes can be quantitatively analyzed by gel permeation chromatography. A comprehensive probability theory on the polydispersity indices of LRP polymers is presented.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. Highly soluble conducting poly(ethylene oxide) grafted at two sites of poly(o-aminobenzyl alcohol) (pages 4756–4764)

      Fengjun Hua and Eli Ruckenstein

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20323

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      Various poly(o-aminobenzyl alcohol) (POABA) copolymers grafted with various poly(ethylene oxide)s (PEOs) were prepared through substitution reactions with various tosylated PEOs at the hydroxide and amine moieties of reduced POABA. The grafted copolymers were very soluble in common polar solvents, such as chloroform, tetrahydrofuran, and dimethylformamide, and the copolymers with longer PEO side chains (number-average molecular weight > 164) were even water-soluble. Their chemical structure is shown to the right.

    2. Influence of electronic effect on catalytic activity of salicylaldiminato nickel(II) complexes (pages 4765–4774)

      Tianzhu Zhang, Dawei Guo, Suyun Jie, Wen-Hua Sun, Ting Li and Xiaozhen Yang

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20242

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      A means of correlation between the activity and the net charge, the metal atom net charge correlation (MANCC), was used to study the catalytic activities of salicylaldiminato Ni(II) catalysts for olefin polymerization or oligomerization. A comparison with the available quantum mechanics/molecular mechanics (QM/MM) calculation data suggests that even without a detailed mechanism, MANCC results mostly agree with QM/MM calculation data. The investigation indicated that the catalytic activities predominantly increase with the net charges on the metal atoms. Consistent experimental results were obtained for four additional complexes synthesized.

    3. Charge transfer interactions in polyesters with a donor-(σ-bridge)-acceptor moiety in the repeating unit (pages 4775–4784)

      Wibren D. Oosterbaan, Veronica E. M. Kaats-Richters, Leonardus W. Jenneskens and Cornelis A. Van Walree

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20291

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      When electroactive donor-σ-bridge-acceptor units are incorporated into a polymer, their behavior differs strongly from that in solution. Not only the photophysics, but also the solid state and thermal properties of the polymer are dominated by interchain donor-acceptor interactions.

    4. Synthesis and characterization of oxidized cellulose (pages 4785–4791)

      Dmitry S. Zimnitsky, Tatiana L. Yurkshtovich and Pavel M. Bychkovsky

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20302

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      Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen (IV) oxide in CCl4. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N2O4 in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated.

    5. Poly[2,7-(9,9-dihexylfluorene)-alt-pyridine] with donor-acceptor architectures: A new series of blue-light-emitting alternating copolymers (pages 4792–4801)

      Shou-Ping Liu, Hardy S. O. Chan and Siu-Choon Ng

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20294

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      A novel series of well-defined alternating poly[2,7-(9,9-dihexylfluorenyl)-alt-pyridinyl] (PDHFP) with donor-acceptor repeat units were synthesized using palladium (0)-catalyzed Suzuki cross-coupling reactions in good to high yields. Meta-linkage (3,5- or 2,6-linkage) of pyridinyl units in the polymer backbone is more favorable to polymer for pure blue emission and prevention of aggregation of polymer chain than para-linkage (2,5-linkage) of the pyridinyl units.

    6. Preparation of magnetic polystyrene latex via the miniemulsion polymerization technique (pages 4802–4808)

      I. Csetneki, M. Kabai Faix, A. Szilágyi, A. L. Kovács, Z. Németh and M. Zrinyi

      Version of Record online: 17 AUG 2004 | DOI: 10.1002/pola.20300

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      Magnetic iron oxide (magnetite, Fe3O4) nanoparticles were encapsulated with polystyrene to give a stable water-based magnetic polymer latex, using the miniemulsion polymerization technique. The resulting magnetic latexes were characterized with transmission electron microscopy (TEM), dynamic light scattering (DLS), vibrating sample magnetometer (VSM) and 57Fe Mössbauer spectroscopy measurements. TEM revealed that all magnetite nanoparticles are embedded in the polymer spheres, leaving no empty polystyrene particles. The DLS measurements exhibited a bimodal size distribution for the particles in the latexes. According to our magnetometry and Mössbauer spectroscopy data the encapsulated magnetite particles conserve their superparamagnetic feature.

    7. Synthesis and surface properties of fluorinated block copolymers containing sulfonic groups (pages 4809–4819)

      Feng Wang, Hong Li, Zhao Bin Zhang, Chun Pu Hu and Shu Sen Wu

      Version of Record online: 19 AUG 2004 | DOI: 10.1002/pola.20221

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      A series of fluorinated block copolymers containing sulfonic groups (PSSF) was successfully prepared. The surface activities of PSSFs in N-methyl pyrrolidone is high. PSSFs and their salts did not appreciably decrease the surface tension of aqueous solution. Furthermore, the surface tensions for two sodium salt systems (PSSF-1-66Na and PSSF-3-54Na) were nearly the same after determination of the critical micelle concentration (cmc), resulting from the aggregation behavior of PSSF on the surface of aqueous solution.

    8. Thermal stability of the fullerene-chain link in 6-arm PS stars with a C60 core (pages 4820–4829)

      Fabrice Audouin, Richard Nuffer and Claude Mathis

      Version of Record online: 19 AUG 2004 | DOI: 10.1002/pola.20305

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      Thermal degradation of 6-arm stars with a C60 core at 100 °C in solution corresponds to a quantitative release of the polystyrene arms through cleavage of the PS-C60 link. It follows a stepwise mechanism where 6-arm stars are converted to 5-arm stars, then to 4-arm stars, and so on. The stability of the PS[BOND]C60 bond increases with decreasing functionality of the star, and the kinetics constants for the first three steps were obtained. Both C[BOND]C bonds in α and β position to C60 can be cut, but the breaking of the direct fullerene-arm bond is favored.

    9. Preparation and characterization of SBA-15 supported iron(II)-bisimine pyridine catalyst for ethylene polymerization (pages 4830–4837)

      Chao Guo, Guo-Xin Jin and Fusong Wang

      Version of Record online: 19 AUG 2004 | DOI: 10.1002/pola.20306

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      Fe catalyst supported on SBA-15 was studied. The supported catalyst can be used for ethylene polymerization with high catalytic activities in the presence of MAO. The higher molecular weight and fibrous morphology of polyethylene were obtained.

    10. Synthesis and characterization of fluorescent poly[fluorene-co-phenylene-1-(di-2-pyridylamine)] copolymer and its Ru(II) complex (pages 4838–4846)

      K. Dinakaran, Chia-Hung Chou, So-Lin Hsu and Kung-Hwa Wei

      Version of Record online: 24 AUG 2004 | DOI: 10.1002/pola.20317

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      2,2′-Dipyridylamine substituted poly(fluorene-co-phenylene) copolymers with different concentrations of dipyridylamine have been synthesized by Suzuki polycondensation. The introduction of dipyridylamine and its ruthenium complex in the polymer significantly improves the photoluminescence efficiency.

    11. Synthesis and characterization of micrometer-sized homo and composite polyacrylonitrile particles of narrow size distribution on the basis of single-step swelling of uniform polystyrene template microspheres (pages 4847–4861)

      Lior Boguslavsky and Shlomo Margel

      Version of Record online: 24 AUG 2004 | DOI: 10.1002/pola.20212

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      A single-step swelling process of uniform micron-sized polystyrene particles has been used to prepare uniform polystyrene/polyacrylonitrile composite particles and polyacrylonitrile particles of controlled properties. Cross-sectional TEM photomicrographs are enclosed.

    12. Reversible addition–fragmentation transfer polymerization of p-nitrophenyl acrylate and synthesis of diblock copolymers poly(p-nitrophenyl acrylate)-b-polystyrene (pages 4862–4872)

      Yong-Chen Hu, Ye Liu and Cai-Yuan Pan

      Version of Record online: 24 AUG 2004 | DOI: 10.1002/pola.20290

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      Poly (p-nitrophenyl acrylate)s with different molecular mass and narrow polydispersity were successfully synthesized by reversible addition-fragmentation transfer (RAFT) polymerization. Although the molecular mass of PNPAs can be controlled by the molar ratio of NPA to RAFT agent and the conversion, a trace of homo-PNPA was found at the early stage of polymerization. The dithiobenzoyl-terminated PNPA obtained was used as a macro chain-transfer agent in the successive RAFT block copolymerization of styrene. After purification by two washings with cyclohexane and nitromethane, the pure diblock copolymers with narrow polydispersity were obtained.

    13. Synthesis and characterization of well-defined diblock and triblock copolymers of poly(N-isopropylacrylamide) and poly(ethylene oxide) (pages 4873–4881)

      Chun-Yan Hong, Ye-Zi You and Cai-Yuan Pan

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/pola.20248

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      Well-defined diblock and triblock copolymers composed of poly(N-isopropylacrylamide) and poly(ethylene oxide) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N-isopropylacrylamide with poly(ethylene oxide) capped with one or two dithiobenzoyl groups as a macrotransfer agent. The block copolymerizations were living in nature.

    14. Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-alkyl-2-pyridylmethanimine as the ligand (pages 4882–4894)

      Huiqi Zhang and Ulrich S. Schubert

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/pola.20289

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      This article describes systematic studies on iron halide mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with N-(n-hexyl)-2-pyridylmethanimine as the ligand, where fast polymerization, linear progress of molecular weights with monomer conversions, and low polydispersities of polymers were achieved under optimal reaction conditions. The figure shows size exclusion chromatography (SEC) traces of a polymer prepared via the iron halide mediated ATRP of MMA, with p-toluenesulfonyl chloride as the initiator [molecular weight of the polymer determined by sec (Mn,SEC) = 10,060 and PDI = 1.18, solid line] and its chain-extended polymer with MMA (Mn,SEC = 41,130 and PDI = 1.38, dotted line).

    15. Reaction control in radical polymerization of di-n-butyl itaconate utilizing a hydrogen-bonding interaction (pages 4895–4905)

      Tomohiro Hirano, Kousuke Higashi, Makiko Seno and Tsuneyuki Sato

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/pola.20293

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      Radical polymerizations of di-n-butyl itaconate (DBI) were examined in the presence of amide compounds. The addition of an equimolar amount of amide compound significantly suppressed the intramolecular chain-transfer reaction that takes place in itaconate polymerization as a side reaction. The NMR analysis revealed that DBI and amide compound formed a mixture of 1:1 complex and 1:2 complex through a hydrogen-bonding interaction. The ESR analysis of polymerization of diisopropyl itaconate (DiPI) and NMR analysis of the obtained poly(DiPI) suggested that the suppression of the intramolecular chain-transfer reaction with the hydrogen-bonding interaction was achieved by controlling the conformation of the side chain at the penultimate monomeric unit of the propagating radical with an isotactic stereosequence.

    16. Investigation of the solid phase synthesis of tyrosine-derived diphenol monomers with resin-bound carbodiimide coupling reagents (pages 4906–4915)

      Anirban Sen Gupta and Stephanie T. Lopina

      Version of Record online: 25 AUG 2004 | DOI: 10.1002/pola.20320

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      Tyrosine-derived “pseudo”-polypeptides have shown significant promise in biomaterial applications. The development of these polymers is dependant upon the convenient synthesis of tyrosine-derived diphenolic monomers. Suitable “solution-phase” methods for the monomer synthesis, using transient activated esters, have been reported previously by Kohn et al. In this paper, an alternate, “solid phase” method for the monomer synthesis using polymer resin bound carbodiimide in a “reverse-Merrifield” sense, is reported. This alternate process made the purification and isolation of the monomer relatively more convenient than the typical “solution phase” processes. Subsequent successful polymerization of the monomers is also reported.

    17. Photopolymerization of acrylamide initiated by the three-component system safranine/triethanolamine/diphenyliodonium chloride: The effect of the aggregation of the salt (pages 4916–4920)

      María L. Gómez, Hernán A. Montejano, María del Valle Bohorquez and Carlos M. Previtali

      Version of Record online: 26 AUG 2004 | DOI: 10.1002/pola.20296

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      The effects of the diphenyliodonium chloride (DPI) concentration on the relative polymerization rate (Rp/Rmath image), relative triplet yield, and light scattering of solutions (Is) have been studied.

    18. Thermal self-initiation of styrene in the presence of TEMPO radicals: Bulk and miniemulsion (pages 4921–4932)

      Gaofeng Pan, E. David Sudol, Victoria L. Dimonie and Mohamed S. El-Aasser

      Version of Record online: 26 AUG 2004 | DOI: 10.1002/pola.20316

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      In styrene bulk and miniemulsion systems, the consumption rate of TEMPO (2,2,6,6,-tetramethyl-1-piperidinyloxy) owing to thermal radical generation was calculated from the length of the induction period (in the absence of initiator) and the increasing total number of polymer chains. Little difference between these two systems was noted in terms of the length of the induction period, which increased linearly with initial TEMPO concentration as shown here. After the induction period, the consumption rate of TEMPO (equivalent to the radical generation rate) was reduced to a lower level, and a faster initial polymerization rate was found in the bulk system compared to the corresponding miniemulsion system.

    19. In situ Fourier transform near infrared spectroscopy monitoring of copper mediated living radical polymerization (pages 4933–4940)

      Vincent Darcos, Sophie Monge and David M. Haddleton

      Version of Record online: 26 AUG 2004 | DOI: 10.1002/pola.20308

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      In situ Fourier transform near infrared (FTNIR) spectroscopy was used to monitor monomer conversion of methacrylic monomers during copper mediated living radical polymerization. This technique proved to be very useful because it allowed for the determination of kinetic parameters.

    20. Direct incorporation of gaseous carbon dioxide into solid-state copolymer containing oxirane and quaternary ammonium halide structure as self-catalytic function (pages 4941–4947)

      Bungo Ochiai, Tokinori Iwamoto, Toyoharu Miyagawa, Daisuke Nagai and Takeshi Endo

      Version of Record online: 27 AUG 2004 | DOI: 10.1002/pola.20311

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      Gaseous carbon dioxide was incorporated into solid-state terpolymers prepared by polymerization of glycidyl methacrylate, N-benzyl-N-[2-(methacryrolroxy)ethyl]-n,n-dimethylammonium bromide, and methyl methacrylate, oxirane moieties in which they were transformed to cyclic carbonate moieties. Terpolymer composition affected the incorporation behavior where the terpolymer with higher oxirane content exhibited higher efficiency of carbon dioxide incorporation.

    21. Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines (pages 4948–4963)

      G. Ullrich, D. Herzog, R. Liska, P. Burtscher and N. Moszner

      Version of Record online: 27 AUG 2004 | DOI: 10.1002/pola.20318

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      Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. Properties of the new photoinitiating systems were investigated by UV spectroscopy and photodifferential scanning calorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance were obtained. Surprisingly, 10-acetyl derivatives 79 and 18 especially doubled the rate of polymerization. Intramolecular reaction was confirmed by photo-differential scanning calorimetry experiments with varying PI concentrations.

    22. Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers (pages 4964–4975)

      François Lavaud, Michel Fontanille and Yves Gnanou

      Version of Record online: 27 AUG 2004 | DOI: 10.1002/pola.20331

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      Sparteine has a beneficial effect in the anionic polymerization of MMA in THF, with a decrease of the extent of termination. The kinetics of polymerization was investigated using adiabatic calorimetry (under high vacuum), which allowed us to study the range of [P*] < 10−4 mo/l. Under these conditions, the extent of termination is much higher than that determined for [P*] ≥ 10−3 mol/l.

    23. Living polymerization of styrene initiated by mercaptan/ε-caprolactam (pages 4976–4993)

      Yu-Hsiang Hu, Chuh-Yung Chen, Chen-Chien Wang, Yao-Hui Huang and Shao-Ping Wang

      Version of Record online: 27 AUG 2004 | DOI: 10.1002/pola.20333

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      The bulk polymerization of styrene initiated by ε-caprolactam (CL) and n-dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, 1H NMR, and 13C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The polymerization rate varies linearly with the concentration of ε-caprolactam and n-dodecyl mercaptan, respectively.

    24. Synthesis and characterization of alkylated N-vinylformamide monomers and their polymers (pages 4994–5004)

      Lianjun Shi, Keri A. Boduch-Lee, John T. Henssler, Eric J. Beckman and Toby M. Chapman

      Version of Record online: 30 AUG 2004 | DOI: 10.1002/pola.20321

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      Procedures have been developed to N-alkylate N-vinylformamide. The N-alkylated derivatives can be polymerized and copolymerize with N-vinylformamide. The copolymers are amphiphilic, those containing N-butyl, N-hexyl, and N-decyl groups demonstrate a critical micelle concentration above which they can solubilize an azo dye of low water solubility. The N-hexyl containing copolymer is shown to stabilize a castor oil in water emulsion. The higher N-alkylated polymers are surprisingly resistant to base hydrolysis. The N-alkylated amides exist in two rotamers about the carbonyl-nitrogen bond, the E isomer favored.

    25. Poly(vinyl acetate-co-dibutyl maleate) latex films in the presence of grafted and post-added poly(vinyl alcohol) (pages 5005–5020)

      Jun Wu, Huxi Li, Mitchell A. Winnik, Rajeev Farwaha and Jude Rademacher

      Version of Record online: 30 AUG 2004 | DOI: 10.1002/pola.20255

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      We describe polymer diffusion in poly(vinyl acetate-co-dibutyl maleate) [P(VAc-DBM)] latex films in the presence of grafted and post-added poly(vinyl alcohol) (PVOH), as monitored by fluorescence resonant energy transfer (ET) experiments. The presence of post-added PVOH (5%) retarded the rate of polymer diffusion, whereas the presence of grafted PVOH significantly increased the polymer diffusion rate. Our data also suggest that under our experimental conditions, the rate of P(VAc-DBM) diffusion will increase with an increase in the degree of PVOH grafting.

  3. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. Aldol addition of dimethylsilyl enolate with alkali metal salt catalyst on solid poly(N,N-dimethylacrylamide) (pages 5021–5025)

      Shin-ichi Yamamoto, Sachika Hayashi, Hidehiko Morita and Osamu Moriya

      Version of Record online: 30 AUG 2004 | DOI: 10.1002/pola.20339

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      Aldol addition in the presence of the resin of poly(N,N-dimethylacrylamide) (PDMA) with alkali metal salt was conducted in a solvent-free condition, and the corresponding adducts were obtained from dimethylsilyl enolates and aldehydes. The results demonstrate that PDMA can form an effective reaction environment.

    2. Solid-supported synthesis of well-defined polymethacrylate with samarium(III) enolate immobilized on polystyrene beads through an acetal-type linker (pages 5026–5029)

      Masayoshi Tanaka, Atsushi Sudo and Takeshi Endo

      Version of Record online: 30 AUG 2004 | DOI: 10.1002/pola.20405

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      A solid-supported samarium enolate, designed to have an acetal-type linker, initiated the polymerization of methyl methacrylate (MMA) in a living anionic fashion. The linker was selectively cleaved at the acetal structure by a treatment with a weak acid, and this produced well-defined poly(MMA).

  4. Erratum

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Erratum
    1. You have free access to this content

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