Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 13

1 July 2009

Volume 47, Issue 13

Pages 3209–3454

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      Synthesis and degradation of biomedical materials based on linear and star shaped polyglycidols (pages 3209–3231)

      Helmut Keul and Martin Möller

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23359

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      Polyethers based on protected glycidols, alkyloxiranes, and tetrahydrofuran were used to prepare multifunctional polymers and heterografted polymer brushes via chemical and enzyme catalyzed reaction. The potential of these multifunctional polyethers for biomedical application with special emphasis on poly(glycidol-graft-caprolactone)-co-glycidol) prepared via enzyme catalyzed grafting of polyglycidols using ε-caprolactone as a monomer and Lipase B from Candida antarctica as a catalyst is presented. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  2. Articles

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    1. Synthesis and characterization of poly(acrylic acid-co-acrylamide)/hydrotalcite nanocomposite hydrogels for carbonic anhydrase immobilization (pages 3232–3240)

      Ya-Tao Zhang, Li-Hai Fan, Tian-Tian Zhi, Lin Zhang, He Huang and Huan-Lin Chen

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23367

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      Porous poly(acrylic acid-co-acrylamide)/hydrotalcite (PAA-AAm/HT) nanocomposite hydrogels were prepared successfully. Then, PAA-AAm/HT nanocomposite hydrogels were used to immobilize carbonic anhydrase, and the CO2 hydration activities of free enzyme and immobilized enzyme were evaluated. Results showed that dried hydrogels disperse uniformly in the form of regular spherical particles (around 100 nm), and the porous structure of hydrogels was also obviously observed. Interestingly, immobilized CA could retain the majority of the enzyme activity, and the porous embedding of hydrogels strengthened the secondary structure stability and thus enhanced enzyme stability in the presence of organic solvent and at high temperature. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Design of controlled releasing system: Synthesis of an amphiphilic copolymer endowed with acid-labile side chains based on quaternarization of amine-containing prepolymer with benzyl halide having acetal moiety (pages 3241–3247)

      Hisatoyo Morinaga, Hiroshi Morikawa, Atsushi Sudo and Takeshi Endo

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23377

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      A new statistical amphiphilic copolymer having acid-labile acetal linkages and quaternary ammonium cations in the side chain was facilely synthesized by quaternarization of tertiary amino side chains of a hydrophilic polymer with benzyl chloride having a geraniol-derived acetal moiety. Under acidic conditions, the acetal moiety of the polymer was gradually hydrolyzed to achieve long-lasting release of geraniol for 9 days (at pH 2) and for more than 30 days (at pH 4). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Preparation, characterization, and properties of fluorinated polyurethanes (pages 3248–3256)

      Guichang Jiang, Xinlin Tuo, Dongrui Wang and Qiang Li

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23386

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      FPUs films were treated in an oxidative solution that has been shown to mimic the effects of the in vivo environment at an accelerated rate. Twenty percent of H2O2 and 0.1 M CoCl2 were used in the oxidative treatment. After immersion in 20% H2O2 and 0.1 M CoCl2 at 37 °C for 5 weeks, the surface of PUs films under scanning electron spectroscopy showed grooves, whereas almost no grooves were observed on FPUs films. A comparison between PUs and FPUs exposed to oxidation is shown. PUs showed signs of deep, aggressive degradation after immersion in 20% H2O2 and 0.1 M CoCl2 at 37 °C for 5 weeks. FPUs was devoid of significant surface degradation after immersion in 20% H2O2 and 0.1 M CoCl2 at 37 °C for 5 weeks.

    4. Preparation of molecularly imprinted polymer microspheres via atom transfer radical precipitation polymerization (pages 3257–3270)

      Baiyi Zu, Guoqing Pan, Xianzhi Guo, Ying Zhang and Huiqi Zhang

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23389

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      The combined use of atom transfer radical polymerization and precipitation polymerization in the molecular imprinting field is described for the first time. The new molecular imprinting approach, namely atom transfer radical precipitation polymerization (ATRPP), has proven to be a general and versatile protocol for the preparation of functional MIP spherical particles with obvious molecular imprinting effects, fast template rebinding kinetics and an appreciable selectivity over structurally related compounds. The unique living chain propagation mechanism in ATRPP leads to MIP microspheres with much larger diameters and significantly higher high-affinity site densities than the MIP submicrospheres prepared via traditional radical precipitation polymerization. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. AlR2Cl/MgR2 combinations as universal cocatalysts for Ziegler–Natta, metallocene, and post-metallocene catalysts (pages 3271–3285)

      Yury V. Kissin, Robert I. Mink, Anita J. Brandolini and Thomas E. Nowlin

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23391

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      Combinations of dialkylaluminum chlorides and dialkylmagnesium compounds at [AlR2Cl]:[MgR2]mol ≥ 2 act as universal cocatalysts for all three presently known types of alkene polymerization catalysts—Ziegler–Natta, metallocene, and post-metallocene. In the case of supported Ti-based Ziegler–Natta catalysts, these cocatalysts produce catalyst systems which are 1.5–2 times more active than the systems containing AlR3 compounds as cocatalysts. Combinations of AlR2Cl/MgR2 cocatalysts and metallocene complexes produce single-center catalyst systems. The same cocatalysts activate numerous post-metallocene Ti complexes containing bidentate ligands of a different nature and produce multicenter catalyst systems of very high activity.

    6. Blue electroluminescence from 3,6-silafluorene-based copolymers (pages 3286–3295)

      Yue-Qi Mo, Xian-Yu Deng, Xi Jiang and Qiu-Hong Cui

      Version of Record online: 20 MAY 2009 | DOI: 10.1002/pola.23393

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      The blue electroluminescence from the 3,6-silafluorene-based copolymers via intrachain energy transfer was reported. The monomer containing vinylene, anthracene, and triarylamine moieties incorporated into the poly(3,6-silafluorene) backbone can form efficient deep-blue emitting copolymers with EL efficiency of 1.1–1.9%. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Synthesis and optoelectronic properties of liquid-crystalline copolymers based on fluorene and triphenylamine-containing oligo(p-phenylenevinylene) derivatives for white light emission (pages 3296–3308)

      Hui Li, Lei Wang, Bin Zhao, Ping Shen and Songting Tan

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23394

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      A series of novel copolymers based on fluorene and triphenylamine-containing oligo(p-phenylenevinylene) derivatives have been designed and synthesized. All of the copolymers exhibit thermotropic liquid crystalline properties and represent the characteristic Schlieren textures in a wide temperature range. A single layer device based on the blend of PF/PF-LOPV05 with the weight ratio of 5:1 emits pure white electroluminescence with CIE coordinates of (0.30, 0.35) at 8 V.

    8. High solubility, low-dielectric constant, and optical transparency of novel polyimides derived from 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenyl-4″-isopropyltoluene (pages 3309–3317)

      Chen-Yi Wang, Guang Li, Xiao-Yan Zhao and Jian-Ming Jiang

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23395

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      A series of novel polyimides containing bulky alkyl pendant groups and noncoplanar structure, were prepared successfully. The obtained polyimides could be quickly soluble in most common solvents at room temperature. Meanwhile, they showed high-optical transparency with λcutoff in the range of 328–353 nm and T450 > 81%. Moreover, these polyimides displayed sufficiently high Tg values beyond 327 °C and low-dielectric constants in the range of 2.49–2.94 at 1 MHz. In comparison with some fluorinated poly(ether imide)s derived from the trifluoromethyl-substituted bis(ether amine)s, the resultant polyimides showed better solubility, lower cutoff wavelength, and higher Tg.

    9. Dual responsive poly(N-isopropylacrylamide) hydrogels having spironaphthoxazines as pendant groups (pages 3318–3325)

      Erandimala U. Kulawardana, Thilini Kuruwita-Mudiyanselage and Douglas C. Neckers

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23397

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      A new dual responsive hydrogel (PNIPAAm-MSp) consisting of a thermoresponsive poly(N-isopropylacrylamide) backbone and photoresponsive spironaphthoxazine pendant groups has been synthesized. Poly(N-isopropylacrylamide) backbone responds to heat and the spironaphthoxazine pendants respond to light. The water absorption with respect to light and heat was investigated. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Self-controlled synthesis of hyperbranched poly(ether-ketone)s from A2 + B3 approach in poly(phosphoric acid) (pages 3326–3336)

      In-Yup Jeon, Loon-Seng Tan and Jong-Beom Baek

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23402

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      Hyperbranched poly(ether-ketone)s (HPEKs) were prepared from hydrophilic A2 and hydrophobic B3 monomers in a hydrophobic reaction medium without gelation. The resultant HPEKs were completely soluble in a variety of common solvents, which was a strong indication that there were no insoluble gels. Thus, it could be concluded the polymer-forming reaction was kinetically controlled up to a maximum conversion. The results could portend that proper selection of monomers and reaction medium would be cost-effective for the preparation of hyperbranched polymers.

    11. Hydroxyl- and amine-terminated hyperbranched polyurethanes using AB2-type azide monomers: Synthesis, characterization, fluorescence, and charge-transfer complexation studies (pages 3337–3351)

      Chickiyan Sivakumar and A. Sultan Nasar

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23404

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      Novel hydroxyl- and amine-terminated hyperbranched polyurethane with and without ether groups were synthesized. It was found that these polymers were fluorescent in 425–525 nm range.

    12. Design, synthesis, and characterization of a partially chlorinated acrylic copolymer for low-loss and thermally stable graded index plastic optical fibers (pages 3352–3361)

      Kotaro Koike, František Mikeš, Yoshiyuki Okamoto and Yasuhiro Koike

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23408

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      As a promising candidate for gigabit optical home and automobile networks, a graded index plastic optical fiber (GI POF) based on a copolymer of methyl α-chloro acrylate (MCA) and 2,2,2-trichloroethyl methacrylate (TCEMA) was investigated. The glass transition temperatures (Tg) of the copolymers were in the range of 133–147 °C and the transmittances of the copolymers were much higher than that of PMMA which has been commonly used as a base material of POF. A suitable GI POF was successfully obtained using the MCA and TCEMA copolymer.

    13. Direct patterning of poly(amic acid) and low-temperature imidization using a crosslinker, a photoacid generator, and a thermobase generator (pages 3362–3369)

      Tomohito Ogura, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23411

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      A positive-type photosensitive polyimide (PSPI) based on poly(amic acid) (PAA), a cross-linker 1,1,1-tris{4-[2-(vinyloxy) ethoxy]phenyl}ethane (TVPE), a photoacid generator (PAG) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-(methylphenyl)acetonitrile (PTMA), and a thermobase generator (TBG) t-butyl 2,6-dimethylpiperidine-1-carboxylate (BDPC) for low-temperature imidization has been developed as a promising material in microelectronics.

    14. Photophysical and electrochemical characterization of new poly(arylene vinylene) copolymers containing quinoline or bisquinoline segments (pages 3370–3379)

      John A. Mikroyannidis, Mihalis Fakis and Ioakim K. Spiliopoulos

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23412

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      Four new fluorescent conjugated poly(arylene vinylene)s incorporating quinoline or bisquinoline segments along the main chain were synthesized by Heck coupling. Their photophysical and electrochemical properties were investigated.

    15. Determination of block size in poly(ethylene oxide)-b-polystyrene block copolymers by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (pages 3380–3390)

      Marion Girod, Michaël Mazarin, Trang N. T. Phan, Didier Gigmes and Laurence Charles

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23414

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      Copolymer hydrolysis allows the block length to be readily obtained from MALDI mass spectra. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Frontal polymerization synthesis and characterization of Konjac glucomannan-graft-acrylic acid polymers (pages 3391–3398)

      Jing Li, Xia Zhang, Jian Chen, Jun Xia, Meihu Ma and Bin Li

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23416

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      Konjac glucomannan-graft-acrylic acid polymer, used as superabsorbent polymers (SAPs), was synthesized by frontal polymerization. Porous structure appeared in SAP, which was readily apparent from the SEM images. Water absorbency of SAP was investigated and most of them displayed high water absorption rate.

    17. Low band gap copolymers based on thiophene and quinoxaline: Their electronic energy levels and photovoltaic application (pages 3399–3408)

      Qiang Peng, Jun Xu and Wenxu Zheng

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23419

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      Low band gap conjugated copolymers containing donor (thiophene)-acceptor (quinoxaline,Qx) were synthesized via Stille coupling polymerization. UV-vis spectra indicated that the increase in the content of quinoxaline units increased the interaction strengthen of the polymer main chains and caused a red-shift in the optical absorbance. Polymer photovoltaic cells (PVCs) were fabricated with the structure of ITO/PEDOT:PSS/active layer/Ca/Al. The results show that the introduction of a proper amount of electron-acceptor groups in the polymer main chains induces an extension of the absorption spectra and improves the photovoltaic properties of the copolymers.

    18. One-pot double click reactions for the preparation of H-shaped ABCDE-type quintopolymer (pages 3409–3418)

      Eda Gungor, Gurkan Hizal and Umit Tunca

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23421

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      We employed for the first time double click reactions: Cu(I) catalyzed azide-alkyne 1,3-dipolar cycloaddition and Diels-Alder (4+2) reactions for the preparation of H-shaped polymer possessing pentablocks with different chemical nature (H-shaped quintopolymer) using one-pot technique. H-shaped quintopolymer consists of poly(ethylene glycol) (PEG)-poly(methylmethacrylate) (PMMA) and poly(ε-caprolactone) (PCL)-polystyrene (PS) blocks as side chains and poly(tert-butylacrylate) (PtBA) as a main chain. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Photochemistry and initiation behavior of phenylethynyl onium salts as cationic photoinitiators (pages 3419–3430)

      Michael Höfer and Robert Liska

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23423

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      Phenyl(phenylethynyl)iodonium hexafluorophosphate and diphenyl(phenylethynyl)sulfonium hexafluorophosphate were synthesized as new photoinitiators for cationic photopolymerization. Quantification of cleanness of the counterion was determined by FTIR analysis with subsequent mathematical peak deconvolution. Steady state photolysis yielded diphenyl sulfide and phenyl(phenylethynyl) sulfide or iodobenzene, respectively, as main photodecomposition products, but no benzene was formed. Photo-DSC experiments confirmed high reactivity as photoinitiators but also sensitization by 9,10-dibutylanthracene, 2-isopropylthioxanthone, and surprisingly also by benzophenone is possible.

    20. Synthesis of stimuli-responsive macroazoinitiators and their use as an inistab toward hairy polymer latex particles (pages 3431–3443)

      Syuji Fujii, Yuichi Kakigi, Motomichi Suzaki, Shin-Ichi Yusa, Masahiro Muraoka and Yoshinobu Nakamura

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23424

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      pH-Responsive macroazoinitiators with central azo unit have been synthesized by atom transfer radical polymerization of tertiary amine methacrylates. Dispersion polymerization of styrene using the poly[2-(diethylamino)ethyl methacrylate] (PDEA) macroazoinitiator as an inistab (initiator + stabilizer) was conducted and near-monodisperse nano-sized polystyrene latex particles with pH-responsive PDEA hair were successfully synthesized. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Locally sulfonated poly(ether sulfone)s with highly sulfonated units as proton exchange membrane (pages 3444–3453)

      Kazuya Matsumoto, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23403

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      Novel locally sulfonated poly(ether sulfone)s with highly sulfonated units were synthesized for proton exchange membranes. The high contrast in polarity between hydrophilic and hydrophobic units enabled high proton conduction under low humidity conditions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Erratum

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      Science and technology of perfluorocyclobutyl aryl ether polymers (page 3454)

      Scott T. Iacono, Stephen M. Budy, Jianyong Jin and Dennis W. Smith Jr.

      Version of Record online: 27 MAY 2009 | DOI: 10.1002/pola.23520

      This article corrects:

      Science and technology of perfluorocyclobutyl aryl ether polymers

      Vol. 45, Issue 24, 5705–5721, Version of Record online: 30 OCT 2007

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