Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 22

15 November 2006

Volume 44, Issue 22

Pages 6505–6657

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid communications
    5. Rapid Communications
    6. Notes
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      Polymer chemistry in flow: New polymers, beads, capsules, and fibers (pages 6505–6533)

      Jeremy L. Steinbacher and D. Tyler McQuade

      Version of Record online: 11 OCT 2006 | DOI: 10.1002/pola.21630

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      We review the union between polymer science and microfluidics. Fluids in microreactors allow the synthesis of a wide range of polymeric materials with unique properties. We begin by discussing the important fluid dynamics that dominate the behavior of fluids on the micrometer scale. We then progress through a comprehensive analysis of the polymeric materials synthesized to date, including soluble, linear polymers, monodisperse, spherical, and irregular microparticles, and biphasic microparticles. We conclude with an overview of the methods used to make microreactors.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid communications
    5. Rapid Communications
    6. Notes
    1. Surface-confined photopolymerization of single- and mixed-monomer systems to tailor the wettability of poly(L-lactide) film (pages 6534–6543)

      Amol V. Janorkar, Sarah E. Proulx, Andrew T. Metters and Douglas E. Hirt

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21700

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      The major objective of this research was to modify the surface characteristics of poly(L-lactide) (PLA) by grafting a combination of hydrophilic polymers to produce a continuum of hydrophilicity. The PLA film was solvent cast and the film surfaces were activated by ultra violet (UV) irradiation. A single monomer or combination of two monomers, selected from vinyl acetate (VAc), acrylic acid (AA), and acrylamide (AAm), were then grafted to the PLA film surface using a UV induced photopolymerization process. The film surfaces resulting from each reaction step were analyzed using ATR-FTIR spectroscopy and contact angle goniometry. Results showed that AAm dominated the hydrophilicity of the film surface when copolymerized with VAc or AA, while the water contact angles for PLA films grafted with poly(vinyl acetate-co-acrylic acid) varied more gradually with feed composition.

    2. Reaction kinetics and microgel particle size characterization of ultraviolet-curing unsaturated polyester acrylates (pages 6544–6557)

      Ahmet Nebioglu and Mark D. Soucek

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21744

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      The effects of a multifunctional monomer and internal and terminal unsaturations on UV free-radical network formation have been investigated. It is proposed that internal double bonds tend to participate in intramolecular reactions, whereas terminal double bonds favor both intermolecular chain-extension reactions and intramolecular cyclization reactions. Intramolecular reactions result in the formation of microgel structures through the encapsulation of reactive monomers and oligomers. As the curing further proceeds, cluster formation via crosslinking between microgels and finally macrogelation occur. Microgel and cluster formation have been confirmed by the monitoring of the UV reaction via time-resolved Fourier transform infrared and dynamic light scattering and by the final morphology of the films.

    3. Modification of carboxyl-functionalized single-walled carbon nanotubes with biocompatible, water-soluble phosphorylcholine and sugar-based polymers: Bioinspired nanorods (pages 6558–6568)

      Ravin Narain, Abdelghani Housni and Lynsay Lane

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21727

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      We report here the successful functionalization of single-walled carbon nanotubes with bioinspired sugar and phosphocholine polymeric structures via surface-initiated atom transfer radical polymerization. The surface-polymer-coated carbon nanotubes have been systematically analyzed with infrared and nuclear magnetic resonance spectroscopy and high-resolution transmission electron microscopy, and there is strong evidence of successful functionalization. The successful aqueous dispersion of the carbon nanotubes also indicates that functionalization has been achieved.

    4. Copolymerization of vinylcyclohexane with ethene and propene using zirconocene catalysts (pages 6569–6574)

      Erkki Aitola, Arto Puranen, Harri Setälä, Sami Lipponen, Markku Leskelä and Timo Repo

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21722

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      The use of vinylcyclohexane (VCH) as a monomer was demonstrated with a series of ansa-metallocene/methylaluminoxane catalysts. As a steric, bulky monomer, VCH homopolymerized slowly, and had low incorporation in ethene and propene copolymerizations, which under the applied conditions was below 3.5 and 2.0%, respectively. Even small amounts of the VCH comonomer in poly(ethene-co-vinylcyclohexane) lowered the melting temperature and crystallinity of the material. For poly(propene-co-vinylcyclohexane), VCH can shape the material properties by introducing less or more order to the polymer matrix depending on the microstructure of polypropene.

    5. Synthesis, characterization, and thermal properties of dendrimer-star, block-comb copolymers by ring-opening polymerization and atom transfer radical polymerization (pages 6575–6586)

      Weizhong Yuan, Jinying Yuan, Mi Zhou and Xiaofeng Sui

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21731

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      The star-block copolymer dendrimer poly(ϵ-caprolactone)-block-poly(2-hydroxyethyl methacrylate) was synthesized by the combination of the ring-opening polymerization of ϵ-caprolactone by initiation with a dendrimer polyester and the atom transfer radical polymerization of 2-hydroxyethyl methacrylate. Then, novel and well-defined dendrimer-star, block-comb copolymers were obtained by the ring-opening polymerization of L-lactide initiated by poly(2-hydroxyethyl methacrylate) blocks. The crystallinity of the poly(ϵ-caprolactone) block in the copolymer was much lower than that of linear poly(ϵ-caprolactone), whereas the crystallizability of the poly(L-lactide) segment was destroyed completely.

    6. Synthesis of well-defined miktoarm star polymers of poly(dimethylsiloxane) by the combination of chlorosilane and benzyl chloride linking chemistry (pages 6587–6599)

      Panagiota Fragouli, Hermis Iatrou, Nikos Hadjichristidis, Takuro Sakurai, Yosuke Matsunaga and Akira Hirao

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21707

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      A series of novel four-arm A2B2 and A2BC and five-arm A2B2C miktoarm star polymers, where A is poly(dimethylsiloxane) (PDMS), B is polystyrene, and C is polyisoprene, have been successfully synthesized by the combination of chlorosilane and benzyl chloride linking chemistry. This strategy is general and versatile and can be applied to the synthesis of complex miktoarm star polymers based on PDMS.

    7. Synthesis of poly(n-butyl acrylate) containing multiblocks with a narrow molecular weight distribution using cyclic trithiocarbonates (pages 6600–6606)

      Ping Lei, Qi Wang, Jian Hong and Yixian Li

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21721

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      The polymerization of n-butyl acrylate in the presence of two cyclic trithiocarbonates (CTTCs) and the synthesis of multiblock poly(n-butyl acrylate) have been investigated. The CTTCs not only can be stepwise incorporated into the polymer chain via reversible addition–fragmentation chain transfer (RAFT) but also can be polymerized into polytrithiocarbonate, which functions as a macro-RAFT agent in turn. Through two kinds of mechanisms, multiblock poly(n-butyl acrylate) containing narrow-polydispersity blocks can be prepared.

    8. Template atom transfer radical polymerization of a diaminopyrimidine-derivatized monomer in the presence of a uracil-containing polymer (pages 6607–6615)

      Huadong Tang, Maciej Radosz and Youqing Shen

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21732

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      Uracil-derivatized monomer 6-undecyl-1-(4-vinylbenzyl)uracil and diaminopyrimidine-derivatized monomer 2,6-dioctanoylamido-4-methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization. The polymerization of DMP in the presence of poly[6-undecyl-1-(4-vinylbenzyl)uracil] (PUVU) as a template had a higher polymerization rate than the polymerization without PUVU, producing a stable and insoluble macromolecular complex, PUVU/poly(2,6-dioctanoylamido-4-methacryloyloxypyrimidine). An X-ray diffraction study confirmed that the complex had strandlike domains.

    9. Synthesis of macroporous polymer rods based on an acrylamide derivative monomer (pages 6616–6623)

      Ruben Dario Arrua, Daniel Serrano, Gustavo Pastrana, Miriam Strumia and Cecilia I. Alvarez Igarzabal

      Version of Record online: 9 OCT 2006 | DOI: 10.1002/pola.21768

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      New macroporous polymer rods were synthesized from an acrylamide derivative monomer [N-acryloyl-tris(hydroxymethyl)aminomethane] and N,N′-methylenebisacrylamide as a crosslinking agent with different porogenic mixtures. In different studies, large pore sizes were reached when the coporogen percentage increased, the reaction temperatures were low, and the crosslinking agent concentration was reduced. Alternatively, a porogenic mixture formed from dimethyl sulfoxide and a 1:1 combination of tetradecanol and poly(ethylene glycol) 6000 as coporogens yielded a rod with a high porosity and pore size. These materials are promising as base supports for different chromatographic processes and as supports for catalysis.

    10. Role of anions in the polymerization of 2,5-dimethoxyaniline in the presence of poly(styrene sulfonic acid) (pages 6624–6632)

      Li-Ming Huang, Guo Cheng Huang and Ten-Chin Wen

      Version of Record online: 12 OCT 2006 | DOI: 10.1002/pola.21745

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      Poly(2,5-dimethoxyaniline) (PDMA)-Ag composite were successfully obtained through the oxidative polymerization of 2,5-dimethoxyaniline (DMA) in poly(styrene sulfonic acid) (PSS) with CH3SO3Ag and AgNO3 as oxidants. In situ UV-Vis results showed that the growth rate of PDMA was strongly affected by CH3SOmath image and NOmath image. Comparing curves a and b in the figure, the main difference can be observed in section II. The growth rate of the polymer formation can be derived from the slope of the linear region of the growth absorbance vs. time profile, showing the faster growth rate by using CH3SO3Ag than AgNO3 as oxidants.

    11. Synthesis and properties of star-shaped polymers by the ring-opening polymerization of cyclic carbonate initiated with a trifunctional, poly(ethylene glycol)-based surfactant (pages 6633–6639)

      Hisatoyo Morinaga, Bungo Ochiai and Takeshi Endo

      Version of Record online: 11 OCT 2006 | DOI: 10.1002/pola.21767

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      Three-armed, amphiphilic block copolymers were synthesized by ring-opening polymerizations of trimethylene carbonate initiated with a poly(ethylene glycol) derivative carrying three hydroxyl groups (polyoxyethylene sorbitan monolaurate) in the absence of any catalyst. The poly(ethylene glycol) and poly(trimethylene carbonate) segments were compatible in the solid state. The amphiphilic copolymers emulsified a mixture of ethyl acetate and water successfully.

  3. Rapid communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid communications
    5. Rapid Communications
    6. Notes
    1. Surprising conversion of nanocomposite hydrogels with high mechanical strength by posttreatment: From a low swelling ratio to an ultrahigh swelling ratio (pages 6640–6645)

      Wei Zhang, Yang Liu, Meifang Zhu, Yu Zhang, Xiaoli Liu, Hao Yu, Yongmei Jiang, Yanmo Chen, Dirk Kuckling and Hans-Juergen P. Adler

      Version of Record online: 12 OCT 2006 | DOI: 10.1002/pola.21749

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      A series of Laponite XLS/polyacrylamide nanocomposite hydrogels (S–M gels) have been successfully prepared by in situ polymerization. It has been discovered for the first time that the properties of nanocomposite gels can be modulated by posttreatment; the swelling ratio of the S–M gels increases greatly with heat posttreatment, up to several hundreds times (water/solid) or higher, much more than that of any other reported nanocomposite gels. The improvement is due to the physical structure changes of the S–M gels. Moreover, S–M–T gels (S–M gels after post-treatment) with an ultrahigh swelling ratio still show excellent resilience under pressure, and they can be regarded as novel elastic superabsorbents.

  4. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid communications
    5. Rapid Communications
    6. Notes
    1. Yttrium(III) complex as a highly active catalyst for lactide polymerization (pages 6646–6651)

      Linda M. Hodgson, Andrew J. P. White and Charlotte K. Williams

      Version of Record online: 17 OCT 2006 | DOI: 10.1002/pola.21743

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      The synthesis, characterization, and X-ray crystal structure of a well-defined yttrium(III) amide complex with the bis(thiophosphinic amide) ligand is reported. The new complex exhibits high rates and good control for lactide polymerization. The polymerization kinetics and mechanism are studied under a range of different conditions, and these show that even under mild conditions this complex exhibits polymerization rates among the fastest known.

  5. Notes

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid communications
    5. Rapid Communications
    6. Notes
    1. You have free access to this content
      Effects of propylene prepolymerization on ethylene/1-hexene and ethylene/1-octene copolymerization with an immobilized metallocene catalyst (pages 6652–6657)

      Madri Smit, Xuejing Zheng, Joachim Loos, John C. Chadwick and Cor E. Koning

      Version of Record online: 12 OCT 2006 | DOI: 10.1002/pola.21566

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      An investigation of the effects of a propylene prepolymerization on ethylene/1-hexene and 1-octene copolymerization with a silica-supported zirconocene catalyst revealed that the prepolymerization not only resulted in an increase in the catalyst activity but also gave copolymers with narrower chemical composition distributions. The positive effects of the prepolymerization were ascribed to a more complete fragmentation of the support particle, as illustrated by the uniform cross section of a polyethylene particle prepared with prepolymerization.

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