Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 13

1 July 2007

Volume 45, Issue 13

Pages 2581–2834

  1. Articles

    1. Top of page
    2. Articles
    1. Stereoregular P(MMA)-clay nanocomposites by metallocene catalysts: In situ synthesis and stereocomplex formation (pages 2581–2592)

      Wesley R. Mariott, Nicole C. Escudé and Eugene Y.-X. Chen

      Version of Record online: 14 MAY 2007 | DOI: 10.1002/pola.22097

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      Stereochemically controlled and crystalline stereocomplex P(MMA)–clay nanocomposites have been synthesized using metallocene complexes of various symmetries and two types of alane-intercalated clay activators.

    2. Electric-field-controlled synthesis of HPMA hydrogels containing self-organized arrays of micro-channels (pages 2593–2600)

      Tedric D. Campbell, Randy P. Washington and Oliver Steinbock

      Version of Record online: 14 MAY 2007 | DOI: 10.1002/pola.22016

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      The hydrogel prepared under the influence of an externally applied electric field reveals a stratified structure interconnected through a porous network (a). Without an electric field however, the morphology of the hydrogel is isotropic and non-patterned (b).

    3. Atrp synthesis of abc lipophilic–hydrophilic–fluorophilic triblock copolymers (pages 2601–2608)

      Raja Shunmugam, Cartney E. Smith and Gregory N. Tew

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22017

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      New ABC triblock copolymers that contain lipophilic, hydrophilic, and fluorophilic blocks are reported. These new block copolymers were synthesized via sequential controlled/living atom transfer radical polymerization. The formation of block copolymers was confirmed by size exclusion chromatography, 1H, and 19F NMR. In direct comparison to the ABC copolymer, the corresponding ABA′ polymer did not produce a gel up to 45 wt % polymer.

    4. Controlled/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under 60Co γ-ray irradiation (pages 2609–2616)

      Haiting Zheng, Daoben Hua, Ruke Bai, Keliang Hu, Lijia An and Caiyuan Pan

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22018

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      We have successfully synthesized a new acyl azide monomer that is stable even when stored for 6.5 h at 50 °C, and we have achieved controlled/living free-radical copolymerizations of the monomer under γ-ray irradiation at room temperature in the presence of benzyl 1H-imidazole-1-carbodithioate with no change in the acyl azide groups. It has been demonstrated that the polymers are stable at the ambient temperature and can be controlled by heating or UV irradiation to form isocyanate polymers, which are very useful precursors for unique polyurethanes and other functional materials.

    5. Multiblock poly(4-vinylpyridine) and its copolymer prepared with cyclic trithiocarbonate as a reversible addition–fragmentation transfer agent (pages 2617–2623)

      Lushuai Zhang, Qi Wang, Ping Lei, Xin Wang, Chaoyang Wang and Lei Cai

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22019

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      The polymerization of 4-vinylpyridine in the presence of a cyclic trithiocarbonate (4,7-diphenyl-[1,3]dithiepane-2-thione) as a reversible addition–fragmentation transfer (RAFT) agent was successfully conducted to synthesize multiblock poly(4-vinylpyridine) with narrow-polydispersity blocks. Two kinds of multiblock copolymers of styrene and 4-vinylpyridine, that is, (ABA)n multi-triblock copolymers with polystyrene or poly(4-vinylpyridine) as the outer blocks, were prepared with multiblock polystyrene or poly(4-vinylpyridine) as a macro-RAFT agent, respectively.

    6. Novel UV-induced photografting process for preparing poly(tetrafluoroethylene)-based proton-conducting membranes (pages 2624–2637)

      Masaharu Asano, Jinhua Chen, Yasunari Maekawa, Takahiro Sakamura, Hitoshi Kubota and Masaru Yoshida

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22021

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      A novel process comprising the UV-induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton-conducting membranes. The significance of this process is that the polystyrene can graft throughout the PTFE films. Even through the degree of grafting is lower than 10%, the proton conductivity of the newly prepared membranes can reach a value similar to that of Nafion. In comparison with γ-ray radiation grafting, UV photografting is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided.

    7. Fabrication of polymer hollow nanospheres by a swelling–evaporation strategy (pages 2638–2645)

      Jie Han, Genping Song and Rong Guo

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22023

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      Poly(o-toluidine) (POT) hollow nanospheres derived from POT nanoparticles have been successfully prepared with the swelling–evaporation strategy. First, POT nanoparticles are suspended and swelled by ethanol. Then, the swollen POT nanoparticles are placed under the ambient temperature and pressure to let the solvent evaporate. During the evaporation process, ethanol inside the POT nanoparticles, together with POT chains, moves outside, creating a void at the center of each POT nanoparticle. The evaporation conditions (e.g., temperature and pressure) and different swelling reagents can be used to tune the size and shell thickness of POT hollow nanospheres. Moreover, the proposed swelling–evaporation strategy has potential applications in the synthesis of hollow nanospheres of other polyaniline derivatives.

    8. Synthesis of poly(acrylic acid)-block-poly(L-valine) hybrid through combined atom transfer radical polymerization, click chemistry, and nickel-catalyzed ring opening polymerization methods (pages 2646–2656)

      A. Sinaga, P. Ravi, T. A. Hatton and K. C. Tam

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22024

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      A combined synthetic approach of Atomic Transfer Radical Polymerization, Click Chemistry, and Nickel catalyzed ring opening polymerization was used to synthesize a new hybrid amphiphilic system between a polyacrylic acid (PAA) synthetic segment, and a hydrophobic beta-sheet forming peptide segment, poly(L-valine). The Click Chemistry was shown as a good alternative for the ω-amino functionalization of polymers since it allows preparation of macroinitiators that are free from deactivating or interfering molecules with degree of functionality of about 90%. Using this approach, PAA-block-L-valine hybrid copolymers with polydispersity index as low as 1.15 can be prepared. This combined approach can potentially be extended for the synthesis of a multitude of other peptide hybrid systems and hence will be of particular interest to the scientific community.

    9. Structure and morphology of nanocomposite films prepared from polyvinyl alcohol and silver nitrate: Influence of thermal treatment (pages 2657–2672)

      S. Clémenson, L. David and E. Espuche

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22020

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      Hybrid organic/inorganic films have been prepared from an aqueous solution of polyvinyl alcohol (PVA) and silver nitrate. Silver nanoparticles have been generated in the PVA matrix by thermal treatment, and the nanostructuration process has been studied. It was shown that the nanoparticles were formed in the PVA amorphous phase. The comparison of the nanoparticles diameter with the amorphous interlammellae distance of the polymer highlighted that the crystalline lamellae acted as a limiting obstacle for the nanoparticle growth at high temperature. At low temperature, the silver nanoparticle growth was also limited by the kinetics of Ag nanostructuration and by the polymer chain mobility.

    10. Synthesis and characterization of hyperbranched polyesters and polyurethane coatings (pages 2673–2688)

      Savita Kumari, Aswini K. Mishra, Dipak K. Chattopadhyay and K. V. S. N. Raju

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22022

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      Polyurethane (PU) coatings are widely used for variety of high-performance applications in today's coating technology. The emerging hyperbranched polymers having three-dimensional morphology have opened a new avenue to tailor the architecture of PU coatings. In the present investigation, a number of hyperbranched polyesters (HBPs) have been prepared and characterized using NMR, MALDI-TOF, and FTIR. These HBPs were converted into NCO-terminated polyurethanes and the moisture-cured films were characterized by FTIR and DMTA.

    11. Synthesis of novel moisture-curable polyurethanes end-capped with trialkoxysilane and their application to one-component adhesives (pages 2689–2704)

      Yukihiro Nomura, Akihiro Sato, Shinichi Sato, Hideharu Mori and Takeshi Endo

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22025

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      Novel polyurethanes end-capped with trimethoxysilane were developed as water-curable materials in which the curing reaction occurred under humid conditions in the presence of dioctyltin diversatate as a curing catalyst. A variety of amine-terminated trimethoxysilane compounds were synthesized by the Michael addition reaction of commercially available 3-aminopropyltrimethoxysilane with acrylates, and the resulting silane endcappers were used to react with isocyanate-terminated polyurethanes, providing polyurethanes end-capped with trimethoxysilane.

    12. Catalyzed chain growth of polyethylene on magnesium for the synthesis of macroalkoxyamines: Application to the production of block copolymers using controlled radical polymerization (pages 2705–2718)

      Ricardo Godoy Lopez, Christophe Boisson, Franck D'Agosto, Roger Spitz, Fernande Boisson, Didier Gigmes and Denis Bertin

      Version of Record online: 16 MAY 2007 | DOI: 10.1002/pola.22026

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      Alkoxyamine end capped polyethylene (PE) chains were synthesized using a direct simple approach consisting in reaction di(polyethylenyl)magnesium (PE-Mg-PE) chains with a range of nitroxides. PE-Mg-PE compounds were prepared by a catalyzed chain growth reaction of ethylene on n-butyloctylmagnesium (BOMg) with a neodymocene complex (C5Me5)2NdCl2Li(OEt2)2. Complete characterizations confirm the introduction of the desired end groups. A poly(ethylene-b-n-butyl acrylate) block copolymer was obtained by controlled radical polymerization mediated by these macroalkoxyamines.

    13. Nonlinear optical properties of regioregular main-chain polyesters (pages 2719–2725)

      R. Centore, P. Riccio, S. Fusco, A. Carella, A. Quatela, S. Schutzmann, F. Stella and F. De Matteis

      Version of Record online: 17 MAY 2007 | DOI: 10.1002/pola.22027

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      A new regioregular, head-to-tail nonlinear optical polyester is shown with d33 = 21 pm/V at 1368 nm.

    14. Synthesis and characterization of model polybutadiene-1,4-b-polydimethylsiloxane-b-polybutadiene-1,4 copolymers (pages 2726–2733)

      Andrés E. Ciolino, Marcelo A. Villar, Enrique M. Vallés and Nikos Hadjichristidis

      Version of Record online: 17 MAY 2007 | DOI: 10.1002/pola.22028

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      Synthesis and Characterization of Model Polybutadiene-1,4-b-Polydimethylsiloxane-b-Polybutadiene-1,4 Copolymers

    15. 1-allyloxy-2-hydroxy-propyl-starch: Synthesis and characterization (pages 2734–2744)

      Annemarie A. M. L. Huijbrechts, Junrong Huang, Henk A. Schols, Barend van Lagen, Gerben M. Visser, Carmen G. Boeriu and Ernst J. R. Sudhölter

      Version of Record online: 17 MAY 2007 | DOI: 10.1002/pola.22029

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      A novel synthetic route to 1-allyloxy-2-hydroxy-propyl-starch was carried out in a heterogeneous alkaline suspension. The starch derivatives were characterized by the determination of the degree of substitution, the location of the substituent on the glucose residues in the starch, and the distribution of the AHP groups along the polymer chain. The granular morphology and the crystallinity of the native starch and derivatives were investigated. [Color figure can be viewed in the online issue, which is available at]

    16. Frontal polymerization with monofunctional and difunctional ionic liquid monomers (pages 2745–2754)

      Zulma Jiménez and John A. Pojman

      Version of Record online: 17 MAY 2007 | DOI: 10.1002/pola.22030

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      We synthesized a series of ionic liquids from the neutralization reaction between trialkylamines and acrylic or methacrylic acid. For the compounds prepared from the unreactive amines, frontal polymerization could not be achieved without the addition of a diacrylate. Monomers prepared from the (2-dimethylamino)ethyl methacrylate could support frontal polymerization. Polymers were comparable to those prepared by batch curing at 75 °C.

    17. Fast degradable poly(L-lactide-co-ε-caprolactone) microspheres for tissue engineering: Synthesis, characterization, and degradation behavior (pages 2755–2764)

      Kalpna Garkhal, Shalini Verma, S. Jonnalagadda and Neeraj Kumar

      Version of Record online: 17 MAY 2007 | DOI: 10.1002/pola.22031

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      Polymeric scaffolds play a crucial role in engineering process of new tissues and effect the cell growth and viability. Thus, low molecular weight PLCL copolymers of various ratios were synthesized and characterized. Microspheres of about 100 μm diameter were prepared for different copolymers and observed for degradation behavior. Copolymers of different thermal, mechanical properties and different degradation behaviors can be prepared by adjusting the composition of copolymers. Various synthesized polymers from this work have been tested in our laboratory as polymeric scaffold for soft tissue engineering.

    18. Synthesis and characterization of norbornene–ethylene–styrene terpolymers with a substituted ansa-fluorenylamidodimethyltitanium-based catalyst (pages 2765–2773)

      Hoang The Ban, Kei Nishii, Yasuo Tsunogae and Takeshi Shiono

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22033

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      High molecular weight norbornene–ethylene–styrene terpolymers were synthesized via incorporation of styrene into vinyl-type norbornene–ethylene copolymers catalyzed by a substituted ansa-fluorenylamidodimethyltitanium catalyst activated with a suitable cocatalyst at room temperature in toluene. The isolation of the terpolymer out of the contaminated homopolymers was carried out by solvent fractionation techniques. The detail characterizations of the terpolymer with GPC, NMR, DSC, and TEM analyses proved that it contained a true random norbornene–ethylene–styrene terpolymer with an amorphous structure.

    19. Synthesis and characterization of maleimide (Co)polymers with pendant benzoxazine groups by photoinduced radical polymerization and their thermal curing (pages 2774–2786)

      Burcin Gacal, Luminita Cianga, Tarek Agag, Tsutomu Takeichi and Yusuf Yagci

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22034

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      A maleimide monomer with benzoxazine and nitrile functionalities, 1-[3-(4-cyano-phenyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine-6-yl]-maleimide (MI-Bz-4CN), was prepared using N-(4-hydroxyphenylmaleimide) (HPMI), formaldehyde, and 4-aminobenzonitrile. Photoinduced radical polymerization was employed to prepare the alternating copolymers of MI-Bz-4CN with styrene (St) at room temperature using ω,ω-dimethoxy-ω-phenylacetophenone (DMPA) as photoinitiator. Monomer reactivity ratios for the studied monomer pair were calculated by using extended Kelen–Tüdos (Ex. K–T) method. Thermal behavior of the alternating copolymers P(MI-Bz-4CN-alt-St) was investigated by thermogravimetrical analysis (TGA) and differential scanning calorimetry (DSC). The ring-opening polymerization of the pendant benzoxazine groups of the copolymers was monitored by DSC and FT-IR studies.

    20. Synthesis of a nanosize copolymer of 3,4-ethylenedioxythiophene with diclofenac and characterization (pages 2787–2796)

      P. Manisankar, C. Vedhi and G. Selvanathan

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22035

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      A nanosize copolymer of 3,4-ethylenedioxythiophene and diclofenac was synthesized by chemical oxidation using ferric chloride and characterized. It showed good electrochromic properties. The probable mechanism of formation is shown.

    21. Synthesis and properties of sulfonated polyimides from homologous sulfonated diamines bearing bis(aminophenoxyphenyl)sulfone (pages 2797–2811)

      Shouwen Chen, Yan Yin, Hidetoshi Kita and Ken-Ichi Okamoto

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22036

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      Sulfonated polyimides derived from three homologous sulfonated diamines bearing bis(aminophenoxyphenyl)sulfone were synthesized. Their properties (especially the water stability) were investigated. The introduction of a sulfonyl group gave poor water stability to the polyimides.

    22. Thermoresponsive hydrogel of poly(glycidyl methacrylate-co-N-isopropylacrylamide) as a nanoreactor of gold nanoparticles (pages 2812–2819)

      Xiaowei Jiang, De'An Xiong, Yingli An, Peiwen Zheng, Wangqing Zhang and Linqi Shi

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22037

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      The poly(glycidyl methacrylate-co-N-isopropylacrylamide) copolymer is crosslinked with diethylenetriamine to form thermoresponsive hydrogel nanospheres with a lower critical solution temperature at about 50 °C. The hydrogel can act as a nanoreactor of gold nanoparticles to produce a thermoresponsive hydrogel/gold nanocomposite. The thermoresponsive nanocomposite can act as a smart and recyclable catalyst. [Color figure can be viewed in the online issue, which is available at]

    23. Novel analytical method for the crosslinking process: Infrared thermographic analysis of the thermally latent cationic polymerization of a spiroorthoester and a bifunctional oxetane for the construction of a low-shrinkage curing system (pages 2820–2826)

      Bungo Ochiai, Tomomi Nagasawa, Yasuhiro Asano, Daisuke Nagai, Atsushi Sudo and Takeshi Endo

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22038

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      The crosslinking copolymerization of a spiroorthocarbonate [2-phenoxymethyl-1,4,6-trioxa-spiro[4.6]undecane (PSOE)] and a bifunctional oxetane [1,4-bis(3-ethyloxetanylmethoxy) benzene] was monitored by the direct temperature measurement of the polymerization mixture by infrared thermography. The increase in the feed ratio of PSOE decreased the exothermicity of the curing. The low exothermicity by PSOE probably originates from its stable propagating species, and this is confirmed by computational calculation.

    24. Computational evaluation of radical ring-opening polymerization (pages 2827–2834)

      Bungo Ochiai and Takeshi Endo

      Version of Record online: 18 MAY 2007 | DOI: 10.1002/pola.22039

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      The tendencies of ring-opening processes in radical ring-opening polymerizations were evaluated by AM1 and PM3 semi-empirical calculations and 6-31G*-level calculations based on the density functional theory (DFT) B3LYP models. Sixteen cyclic monomers bearing vinyl or exomethylene groups were categorized into ring-opening and no-ring-opening monomers by the evaluation of the differences of the internal energies and the lengths of the cleaving bonds between the ground states of the initial radicals and the activated states in the ring-opening processes. Although the semi-empirical calculations not parameterized to radical reactions resulted in the moderate categorization of the ring-opening monomers, the DFT calculation clearly distinguished the ring-opening and no-ring-opening monomers.