Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 43 Issue 16

15 August 2005

Volume 43, Issue 16

Pages 3461–3717

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      Cylindrical polymer brushes (pages 3461–3481)

      Mingfu Zhang and Axel H. E. Müller

      Article first published online: 28 JUN 2005 | DOI: 10.1002/pola.20900

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      Cylindrical polymer brushes represent an important type of branched polymer. Their regular multibranched structure results in peculiar properties, such as high main-chain stiffness, which may lead to the formation of liquid-crystalline phases. By varying the side-chain length, solvent, pH, temperature, and counterion, one can tune the size and/or shape of a polymer brush. As one application, cylindrical polymer brushes with a core–shell structure have been used as templates for the synthesis of semiconducting and magnetic nanowires.

  2. Articles

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    1. Study on siloxane-modified polyurethane dispersions from various polydimethylsiloxanes (pages 3482–3490)

      Ruei-Shin Chen, Chih-Jen Chang and Yih-Her Chang

      Article first published online: 28 JUN 2005 | DOI: 10.1002/pola.20805

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      A series of PUDs containing hydrophobic PDMS was successfully synthesized. Hydrophobic PDMS was introduced into the PU chain either based on random distribution or through the block segment arrangement, which made their casting films show different mechanical properties and siloxane distribution. The contact angle and mechanical properties of the formed membranes for the different PDMS content of PUD were investigated. The composition-property relationship of PDMS-PUD was also established. Some PDMS-PUD films showed a peau-like surface, because the microphase separation and migration of PDMS-PUD films were great.

    2. Water-swollen highly oxygen permeable membranes: Analytical technique and syntheses (pages 3491–3501)

      G. Erdodi and J. P. Kennedy

      Article first published online: 28 JUN 2005 | DOI: 10.1002/pola.20791

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      A generally accepted method for the determination of high oxygen permeabilities (Dk >100 barrers) of water-immersed membranes is unavailable. We designed and developed a generally applicable method, together with simple equipment, to measure the oxygen permeability up to Dk ∼800 barrers of highly oxygen permeable membranes in contact with water. A theory of the methodology is also presented, giving particular attention to the boundary layer effect and the edge effect. The practical applicability of our technique is demonstrated by preparing and using highly oxygen permeable water-logged membranes, such as polydimethylsiloxane and polysiloxane copolymers important for medicine.

    3. Hyperbranched polymers generated from oxyanionic vinyl polymerization of commercially available methacrylate inimers (pages 3502–3509)

      Zhifeng Jia and Deyue Yan

      Article first published online: 28 JUN 2005 | DOI: 10.1002/pola.20806

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      Hyperbranched polymethacrylates with high molecular weight were synthesized by means of the self-condensing vinyl oxyanionic polymerization of commercially available monomers, including hydroxyethyl methacrylate and poly(ethylene glycol) methacrylate. The initiator used was the complex of potassium hydride with 18-crown-6. Only oligomer could be obtained in the absence of 18-crown-6. So the coordinate reagent, 18-crown-6, played an important role in the polymerization. This finding seems significant for the preparation of high molecular weight hyperbranched polymers through self-condensing vinyl oxyanionic polymerization. In addition, the ratio of initiator to monomer significantly affects the architecture of the resultant polymer based on a proton transfer process.

    4. Advanced flame-retardant epoxy resins from phosphorus-containing diol (pages 3510–3515)

      M. José Alcón, Gemma Ribera, Marina Galià and Virginia Cádiz

      Article first published online: 28 JUN 2005 | DOI: 10.1002/pola.20856

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      Phosphorus-containing epoxy systems were prepared from isobutylbis(hydroxypropyl)phosphine oxide (IHPO) and diglycidyl ether of bisphenol A (DGEBA). Diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphonate (Fyrol 6) could not be incorporated into the epoxy backbone by a reaction with either epichlorohydrin or DGEBA because intramolecular cyclization took place. The curing behavior of the IHPO–DGEBA prepolymer with two primary amines was studied, and materials with moderate glass-transition temperatures were obtained. V-0 materials were obtained when the resins were tested for ignition resistance with the UL-94 test.

    5. Synthesis and characterization of a poly(N-isopropylacrylamide) with β-cyclodextrin as pendant groups (pages 3516–3524)

      Yu-Yang Liu, Xiao-Dong Fan and YA-Bing Zhao

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20836

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      A novel linear poly(N-isopropylacrylamide) (PNIPA) with β-cylodextrin (β-CD) moiety (PNIPA-β-CD) was synthesized by the conjugation of β-CD carrying amino groups (EDA-β-CD) onto PNIPA with epoxy groups [P(NIPA-co-GMA)]. PNIPA-β-CD can not only respond to temperature stimuli but also include guest molecules. Lower critical solution temperature (LCST) of aqueous PNIPA-β-CD solution is similar to that of PNIPA. The association constant (Ka) for PNIPA-β-CD with methyl orange (MO) is 2.4 × 103 L mol−1 at pH 1.4, which is comparable to that of EDA-β-CD (Ka = 2.9 × 103 L mol−1).

    6. Photofabrication of surface relief gratings from azobenzene containing perfluorocyclobutane aryl ether polymer (pages 3525–3532)

      Chaemin Chun, Jieun Ghim, Mi-Jeong Kim and Dong Yu Kim

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20812

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      An azobenzene based perfluorocyclobutane (PFCB) aryl ether polymer, poly[4-(phenylazo)triphenylamine-1,2-hexafluorocyclobutyl ether] (PPF), was synthesized using a palladium catalyzed amination reaction and the 2π + 2π cyclodimerization of 4-[(trifluorovinyl)oxy]bromobenzene. The PFCB polymer, PPF, contains both azobenzene groups, which show photoinduced dynamic behavior and PFCB rings with a high content of fluorine. This polymer permits the efficient, rapid growth of diffraction efficiency, and the holographic surface relief grating was successfully inscribed on PPF thin films with regularly defined grating structures when illuminated with interference beams.

    7. Anionic polymerization of n-hexyl isocyanate with monofuctional initiators. Synthesis of well-defined diblock copolymers with styrene and isoprene (pages 3533–3542)

      Georgia Zorba, Aggelos Vazaios, Marinos Pitsikalis and Nikos Hadjichristidis

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20831

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      Several monofunctional initiators were employed for the polymerization of n-hexyl isocyanate (HIC) in THF at −98°C. The presence of several additives, such as LiBPh4, NaBPh4 and crown ether 18C6 was evaluated. By using benzyl sodium/NaBPh4 system, well-defined block copolymers of HIC with styrene or isoprene were synthesized for the first time.

    8. Synthesis of poly(vinylidene fluoride) (PVdF)/silica hybrids having interpenetrating polymer network structure by using crystallization between PVdF chains (pages 3543–3550)

      Tomoki Ogoshi and Yoshiki Chujo

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20833

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      Transparent poly(vinylidene fluoride) (PVdF)/silica hybrids were obtained by using an in-situ interpenetrating polymer network (IPN) approach. The simultaneous formation of PVdF gel resulting from the physical cross-linking and silica gel from sol–gel process prevented the aggregation of PVdF in silica gel matrix and enabled the nanometer scale dispersion of PVdF in silica gel matrix.

    9. Synthetic and characterization aspects of dimethylaminoethyl methacrylate reversible addition fragmentation chain transfer (RAFT) polymerization (pages 3551–3565)

      Medhi Sahnoun, Marie-Thérèse Charreyre, Laurent Veron, Thierry Delair and Franck D'Agosto

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20813

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      2-Cyanoprop-2-yl dithiobenzoate (CPDB) mediated RAFT polymerization of dimethylaminoethyl methacrylate (DMAEMA) was carried out in dioxane at 90 °C. The influence of several parameters was evaluated with regards to conversion and polymerization duration, as well as control of molar mass and molar mass distributions. Characterization of well-controlled PDMAEMA samples has been performed by size exclusion chromatography (SEC), proton NMR spectroscopy, and matrix assisted laser desorption ionization time of flight mass spectrometry. Finally, a chain extension experiment was evaluated with regard to living features.

    10. High molecular weight monodisperse polystyrene microspheres prepared by dispersion polymerization, using a novel bifunctional macromonomer (pages 3566–3573)

      Hyejun Jung, So Yeoun Kim, Kangseok Lee, Byung H. Lee, Sang Eun Shim and Soonja Choe

      Article first published online: 30 JUN 2005 | DOI: 10.1002/pola.20827

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      A novel macromonomer of vinyl-terminated bifunctional polyurethane was synthesized and applied to the dispersion polymerization of styrene as the reactive stabilizer and grafting agent. The monodisperse polystyrene microspheres having the average diameter 1.2 μm and the high molecular weight of 501,300 g/mol were obtained with 20 wt% macromonomer via dispersion polymerization.

    11. Alternating π-conjugated block copolymers with precise block length (pages 3574–3587)

      Jörg Schappel, Kathrin Schmidt and Elisabeth Klemm

      Article first published online: 5 JUL 2005 | DOI: 10.1002/pola.20826

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      We report the synthesis, characterization, and photophysical properties of new alternating block copolymers with a precise block length. The copolymers consist of oligo(p-phenyleneethynylene) as an electron-rich component and 1,4-bis(2-phenylene-2-cyanovinylene)benzene (P3), 2,6-bis(2-pyridinylene-ethynylene)pyridine (P4), or 2,5-bis(2-pyridinylene-ethynylene)pyridine (P5) as an electron-poor component and have been obtained through the Sonogashira reaction. The absorption and emission behavior of P3 (maximum absorption wavelength = 446 nm and maximum emission wavelength = 540 nm) in solution is equivalent to that of poly(cyano-phenylenevinylene) (CN-PPV). For P4 and P5, a small Stokes Shift of approximately 40 nm and a small quantum yield characterize the emission behavior.

    12. Poly(caprolactone-co-lactide)/perfluoropolyether block copolymers: Synthesis, thermal, and surface characterization (pages 3588–3599)

      Roberta Bongiovanni, Giulio Malucelli, Massimo Messori, Francesco Pilati, Aldo Priola, Claudio Tonelli and Maurizio Toselli

      Article first published online: 5 JUL 2005 | DOI: 10.1002/pola.20797

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      Poly[(caprolactone-co-lactide)-b-perfluoropolyether-b-(caprolactone-co-lactide)] copolymers (TXCLLA) were prepared by ring-opening polymerization of D,L-dilactide (LA2) and caprolactone (CL) in the presence of α,ω-hydroxy terminated perfluoropolyether (Fomblin Z-DOL TX) as macroinitiator and tin(II) 2-ethylexanoate as catalyst. 1H NMR analysis showed that LA2 is initially incorporated into the copolymer preferentially with respect to CL. A blocky structure of the polyester segment was also indicated by the sequence distribution analysis of the monomeric units. Differential scanning calorimetry analysis showed the compatibility between poly(lactide) (PLA) and poly(caprolactone) (PCL) blocks inside the amorphous phase with glass-transition temperature values increasing from −60 to −15 °C by increasing the PLA content. Copolymers with high average length of CL blocks were semicrystalline with a melting temperature ranging from +35 to +47 °C. Surface analysis showed a high surface activity of TXCLLA copolymers with values of surface tension independent from the PLA/PCL content and very close to those of pure TX.

    13. About crosslinking of low molecular weight ethylene-propylene(-diene) copolymer-based artificial latices (pages 3600–3615)

      Delphine L. Tillier, Jan Meuldijk, Pieter C. M. M. Magusin, Alex M. van Herk and Cor E. Koning

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20807

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      Crosslinking of artificial latices based on EPM and/or EPDM has not thoroughly been studied yet. Moreover, it is a prerequisite for the formation of a poly(methyl methacrylate) shell. Therefore, the aim of this article is to improve the general understanding of the chemistry involved in the crosslinking process. This work especially emphasizes the influence of the initiation method, that is, by a peroxide or a pulsed electron-beam, on crosslinking efficiency. The efficiency of various peroxides is also reported. The incorporation of a coagent, for example, divinylbenzene, into the EP(D)M phase was studied on a microscopic level by solid-state 13C and 1H NMR. The efficiency of crosslinking initiated by a pulsed electron-beam was improved to a great extent by the presence, in the aqueous phase, of potassium nitrosodisulfonate, also referred to as Fremy salt. MALDI-TOF-MS was used to determine the influence of electron-beam irradiation on the chemical stability of surfactants.

    14. Preparation of gradient copolymers via ATRP using a simultaneous reverse and normal initiation process. I. Spontaneous gradient (pages 3616–3622)

      Ke Min, Mei Li and Krzysztof Matyjaszewski

      Article first published online: 5 JUL 2005 | DOI: 10.1002/pola.20809

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      Spontaneous gradient copolymers were prepared in both bulk and miniemulsion systems via ATRP utilizing a simultaneous reverse and normal initiation process. The compositions of the gradient copolymers produced in miniemulsion systems were similar to those generated in bulk.

    15. Preparation of polymethylsilsesquioxanes by the base-catalyzed hydrolytic polycondensation of triisopropoxy(methyl)silane (pages 3623–3630)

      Takahiro Gunji, Satoshi Tanikawa, Koji Arimitsu and Yoshimoto Abe

      Article first published online: 5 JUL 2005 | DOI: 10.1002/pola.20838

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      Base-catalyzed controlled hydrolytic polycondensation of triisopropoxy(methyl)silane (TMIPS) provided polymethylsilsesquioxanes with the molecular weights Mw from 2800–88,300 depending on the reaction molar ratios of water and tetrabutylammonium hydroxide to MTIPS. They were soluble in common organic solvents, stable to self-condensation, and provided coating films, for which dielectric constant was 2.6.

    16. Synthesis of gold–poly(methyl methacrylate) core–shell nanoparticles by surface-confined atom transfer radical polymerization at elevated temperature (pages 3631–3642)

      Atanu Kotal, Tarun K. Mandal and David R. Walt

      Article first published online: 8 JUL 2005 | DOI: 10.1002/pola.20853

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      Surface-confined atom transfer radical polymerization (ATRP) was used to prepare gold nanoparticle–poly(methyl methacrylate) (GNP–PMMA) core–shell particles at elevated temperature. First, gold nanoparticles (GNPs) were prepared in the presence of 11-mercapto-1-undecanol; this was followed by exchange with 3-mercaptopropyltrimethoxysilane and hydrolysis with hydrochloric acid. The resulting crosslinked silica-primer layer was reacted with the initiator [(chloromethyl)phenylethyl] trimethoxysilane. ATRP was conducted on the Cl-terminated GNPs at elevated temperatures. The rates of polymerization with the initiator-modified GNPs exhibited first-order kinetics with respect to the monomer, and the number-average molecular weight of the cleaved graft poly(methyl methacrylate) increased linearly with the monomer conversion. A transmission electron microscopy image of the GNP–PMMA nanoparticles revealed a core–shell structure with a uniform polymer shell, and the shell thickness increased with increasing polymerization time.

    17. Thermoresponsive micelles from well-defined block copolymers synthesized via reversible addition–fragmentation chain transfer polymerization (pages 3643–3654)

      Bo Liu and Sébastien Perrier

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20785

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      Thermally responsive micelles formed in water by the self-assembly of poly(N-isopropylacrylamide-b-N,N′-dimethylacrylamide), produced by reversible addition–fragmentation chain transfer (RAFT) polymerization, were studied. The drug loading capacity was illustrated with the use of the solvatochromic Reichardt's dye and measured by ultraviolet–visible.

    18. Silicon surface modification with trialkoxysilyl-functionalized star-shaped polymers (pages 3655–3666)

      Kalpana Viswanathan, Timothy E. Long and Thomas C. Ward

      Article first published online: 12 JUL 2005 | DOI: 10.1002/pola.20800

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      Synthesis of trimethoxysilane end-capped linear polystyrene (PS), star-branched PS and subsequent silicon (Si) surface modification with linear and star polymers are described. The “grafting to” approach was used to modify surfaces with polymers of different topologies. AFM analysis of the resulting surfaces showed that star-PS modified surfaces present a very different surface topography compared to linear polymers of comparable Mn. Comparison of the film properties of the star and the linear PS modified surfaces with their respective chain dimensions in solution indicated that the star PS assumed mushroom-like conformation and the linear polymer chains were in the brush regime.

    19. Syntheses of trimethoxysilyl-endcapped polylactones via 3-mercaptopropyl trimethoxysilane (pages 3667–3674)

      Hans R. Kricheldorf, Heiko Hachmann-Thiessen and Gert Schwarz

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20815

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      A new synthetic approach to trimethoxysilyl-endcapped polylactones is described, which may serve as biodegradable adhesives, glues, coatings, or gels.

    20. Methods for the surface functionalization of γ-Fe2O3 nanoparticles with initiators for atom transfer radical polymerization and the formation of core–shell inorganic–polymer structures (pages 3675–3688)

      Stefanie M. Gravano, Randy Dumas, Kai Liu and Timothy E. Patten

      Article first published online: 12 JUL 2005 | DOI: 10.1002/pola.20823

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      ATRP initiator-containing, carboxylic acid capped γ-Fe2O3 nanoparticles were prepared via two methods: the “functional group interchange” method and the ligand exchange method. Styrene was then polymerized directly off of γ-Fe2O3 nanoparticles yielding hybrid core/shell structures. Measurements of the magnetic properties of the samples demonstrated that the magnetism of the core γ-Fe2O3 nanoparitcle did not change during performance of the chemical transformations.

    21. Syntheses of 12-arm star polymers and star diblock copolymers by nitroxide-mediated radical polymerization using dendritic dodecafunctional macroinitiators (pages 3689–3700)

      Yozo Miura and Hiroyuki Dote

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20814

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      TEMPO-mediated radical polymerizations of styrene were carried out at 120 °C using dendritic dedecafunctional macroinitiators, and 12-arm star polymers (star-12) with narrow polydispersities of Mw/Mn = 1.06–1.26 were obtained. Using star-12 as the macroinitiator TEMPO-mediated radical polymerization of 4-vinylpyridine was carried out, and well-defined poly(St)-b-poly(4-VP) 12-arm star diblock copolymers with Mw/Mn = 1.18–1.19 were obtained.

  3. Rapid Communications

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    1. Optically active polyacetylene: Synthesis and helical conformation of a poly(phenylacetylene) carrying L-alanyl-L-alanine pendants (pages 3701–3706)

      Lo Ming Lai, Jacky W. Y. Lam, Kevin K. L. Cheuk, Hermans H. Y. Sung, Ian D. Williams and Ben Zhong Tang

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20818

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      A phenylacetylene carrying a chiral L-alanine dipeptide moiety has been synthesized, and it has been polymerized by (2,5-norbornadiene)rhodium(I) chloride dimmer {[Rh(nbd)Cl]2} into a high-molecular-weight polymer in a high yield. The polymer chain takes a helical conformation with preferred handedness, which can be tuned by the solvent and temperature.

    2. Early transition metal catalyzed aqueous emulsion copolymerization: Copolymerization of styrene and methyl methacrylate by Cp2TiCl2 in aqueous medium (pages 3707–3710)

      Braja N. Patra and Manish Bhattacharjee

      Article first published online: 6 JUL 2005 | DOI: 10.1002/pola.20829

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      An early transition metal metallocene compound, Cp2TiCl2, with an anionic surfactant, sodium n-dodecyl sulfate (SDS), as emulsifier has been found to be an effective catalyst for copolymerzation of a polar monomer, methyl methacrylate (MMA), and an α-olefin, styrene, and afford high molecular weight copolymer with low molecular weight distribution.

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      Synthesis of a novel cyclic 5-membered dithiocarbonate (DTC) having hydroxy group and its application to terminal functionalization of polyurethane (pages 3711–3717)

      Suguru Motokucho, Yoshiteru Itagaki, Atsushi Sudo and Takeshi Endo

      Article first published online: 12 JUL 2005 | DOI: 10.1002/pola.20872

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      A novel 5-membered cyclic dithiocarbonate (DTC) having a hydroxy group, 5-hydroxymethyl-1,3-oxathiolane-2-thione (DTC-OH), was synthesized from glycidol. On the basis of the highly efficient reaction of its hydroxyl group with isocyanate, a polyurethane having isocyanate terminals was modified with DTC-OH into a new type of polyurethane prepolymer having DTC-terminals, which was highly reactive with amines but tolerant to moisture.