Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 23

1 December 2010

Volume 48, Issue 23

Pages 5271–5641

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. Synthesis and unexpected electrochemical behavior of the triphenylamine-based aramids with ortho- and para-trimethyl-protective substituents (pages 5271–5281)

      Hung-Ju Yen, Shiue-Ming Guo and Guey-Sheng Liou

      Article first published online: 24 SEP 2010 | DOI: 10.1002/pola.24326

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      Two series of new organosoluble polyamides with methyl-substituted triphenylamine (MeTPA) units showing anodically electrochromic characteristic were prepared from the phosphorylation polyamidation reactions of two diamine monomers, 4,4′-diamino-2″,4″,6″-trimethyltriphenylamine (Me3TPA-diamine) and 4,4′-diamino-4″-methyltriphenylamine (MeTPA-diamine), with various dicarboxylic acids, respectively. The unexpected electrochemical behavior of higher oxidation potential and lower electrochemical stability of Me3TPA-polyamides I than MeTPA corresponding polymers could be attributed to the higher steric hindrance of ortho-substituents in Me3TPA moieties, thus made the resonance stabilization of cation radical much more difficult for the Me3-substituted phenyl ring.

    2. Poly-(ε-caprolactone) (PCL) and poly(hydroxy-butyrate) (PHB) blends containing seaweed fibers: Morphology and thermal-mechanical properties (pages 5282–5288)

      Arianna Barghini, Vassilka I. Ivanova, Syed H. Imam and Emo Chiellini

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24327

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      The marine seaweed Ulva Armoricana and the biodegradable polymers PHB and PCL were processed by compression molding to obtain some laminates. The SEM images showed a fiber dispersion, the presence of damages in the polymeric matrix and the poor compatibility between the two materials as shown by the visible absence of the adhesion at the interface for polymeric composites. The thermogravimetric analysis (TGA) confirms the presence of an high amount of siliceous material. The elongation at break (EB) and ultimate tensile strength (UTS) find a good agreement with the increasing amount of algal fiber loading and the composite fragility.

    3. One-pot enzymatic route to tetraallyl ether functional oligoesters: Synthesis, UV curing, and characterization (pages 5289–5297)

      Magnus Eriksson, Antoine Boyer, Loris Sinigoi, Mats Johansson, Eva Malmström, Karl Hult, Stacy Trey and Mats Martinelle

      Article first published online: 1 OCT 2010 | DOI: 10.1002/pola.24328

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      An enzymatic one-pot route in bulk was utilized to synthesize tetraallyl ether (tAE) functional polyesters of targeted molecular weights (from 1300 to 3300 g mol−1) based on divinyl adipate, 1,4-butanediol and trimethylolpropane diallyl ether using the catalyst, lipase B from Candida antarctica. The enzyme catalyzed reaction reached completion (>98% conversion based on all monomers) within 24 h and the resulting polymers were photopolymerized, to form homopolymer networks and combined with thiol functional monomers (dithiol, tetrathiol) in a 1:1 ratio thiol-ene reaction. High conversions (96–99% within detection limits) were found for all thiol-ene films as determined by FT-Raman spectroscopy.

    4. Accelerating effects of N-aryl-N′,N′-dialkyl ureas on epoxy-dicyandiamide curing system (pages 5298–5305)

      Xiang Dong Liu, Mika Kimura, Atsushi Sudo and Takeshi Endo

      Article first published online: 1 OCT 2010 | DOI: 10.1002/pola.24329

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      It was demonstrated that secondary amine is produced by thermal dissociation of N-aryl-N′,N′-disubstituted urea, further reacts with epoxy to produce tertiary amine, and accelerates the epoxy-DICY system to an autocatalytic cure process. The secondary amine released from the urea is the most important factor for the acceleration, which more compact amines give more active cure reactions.

    5. Synthesis of main chain polymeric benzophenone photoinitiator via thiol-ene click chemistry and Its use in free radical polymerization (pages 5306–5312)

      Gokhan Temel, Nurcan Karaca and Nergis Arsu

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24330

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      Main chain polymeric benzophenone photoinitiator (PBP) was synthesized by using “Thiol-ene Click Chemistry” procedure. PBP as a polymeric photoinitiator presented excellent absorption properties compared to the molecular initiator BP. According to phosphorescence lifetime, the lowest triplet state of PBP has an n-π* nature. The initiation efficiency of PBP for polymerization of hexanedioldiacrylate is much higher than for the formulation consisting of BP.

    6. Synthesis of 4μ-PS2PEO2, 4μ-PS2PCL2, 4μ-PI2PEO2, and 4μ-PI2PCL2 star-shaped copolymers by the combination of glaser coupling with living anionic polymerization and ring-opening polymerization (pages 5313–5321)

      Guowei Wang, Xiaoshan Fan and Junlian Huang

      Article first published online: 1 OCT 2010 | DOI: 10.1002/pola.24331

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      The 4μ-A2B2 star-shaped copolymers were synthesized by a combination of Glaser coupling with living anionic polymerization (LAP) and ring-opening polymerization (ROP) mechanisms successfully. This work provided a versatile strategy for the preparation of 4μ-A2B2 star-shaped copolymers with various compositions such as PI, PS, PEO, and PCL.

    7. Incorporation of fluorene-based emitting polymers into silica (pages 5322–5328)

      Ayumi Miyao, Yuta Mori, Takahiro Uno, Takahito Itoh, Takayuki Yamasaki, Akira Koshio and Masataka Kubo

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24332

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      Polyfluorene copolymers with pendant hydroxyl groups were prepared and incorporated into silica to give homogeneous organic/inorganic hybrids by using tetraethoxysilane and perhydropolysilazane as silica precursors. Photoluminescence spectra of these hybrids suggested that emitting polymers were dispersed in silica matrix retaining their π-conjugated structures.

    8. Controlled polymerization of methacrylates at ambient temperature using trithiocarbonate chain transfer agents via SET-RAFT–cyclohexyl methacrylate: A model study (pages 5329–5338)

      N. Haridharan, K. Ponnusamy and R. Dhamodharan

      Article first published online: 1 OCT 2010 | DOI: 10.1002/pola.24333

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      Controlled radical polymerization of cyclohexyl methacrylate at ambient temperature, using various chain transfer agents is successfully demonstrated via SET-RAFT. A novel, fluorescein-based initiator, novel fluorescent chain transfer agent (CTA), and two other trithiocarbonate CTAs comprising of butane thiol with cyano and carboxylic acid as the end group were synthesized and characterized. The polymerization is observed to be uncontrolled under SET and less controlled under ATRP condition and better controlled under SET-RAFT at ambient temperature. It is observed that block copolymers produced from P(CHMA) macroinitiators synthesized via SET-RAFT result in lower PDI in comparison with those synthesized via ATRP.

    9. Ring-opening polymerization of β-butyrolactone catalyzed by efficient magnesium and zinc complexes derived from tridentate anilido-aldimine ligand (pages 5339–5347)

      Yi-Chang Liu, Chia-Her Lin, Bao-Tsan Ko and Rong-Ming Ho

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24334

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      The ring-opening polymerization of β-butyrolactone catalyzed by efficient catalysts 2 and 3 in the presence of 9-anthracenemethanol or polyethylene glycol methyl ether was fully investigated. The catalytic system of complex 3 has demonstrated good activity and excellent control of molecular weight to produce PHB homopolymer, PHB-b-PCL, and PEG-b-PHB copolymers.

    10. Highly near-infrared photoluminescence from aza-borondipyrromethene-based conjugated polymers (pages 5348–5356)

      Ryousuke Yoshii, Atsushi Nagai and Yoshiki Chujo

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24335

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      Near-infrared emissive conjugated polymers were prepared by palladium-catalyzed Sonogashira polymerization of diiodobenzene-functionalized aza-borondipyrromethene (Aza-BODIPY) monomers with 1,4-diethynyl-2,5-dihexadecyloxybenzene or 3,3″-didodecyl-2,2″-diethynyl-5,5″-bithiophene. The polymers efficiently emitted near-infrared light at 753∼777 nm with high and narrow emission bands in this near-infrared region (ϕF = 5∼24%).

    11. Acceleration effect of N-allyl group on thermally induced ring-opening polymerization of 1,3-benzoxazine (pages 5357–5363)

      Hiroaki Oie, Atsushi Sudo and Takeshi Endo

      Article first published online: 29 SEP 2010 | DOI: 10.1002/pola.24338

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      N-Allyl-1,3-benzoxazine underwent the thermally induced ring-opening polymerization much faster than N-(n-propyl)-1,3-benzoxazine with a sterically comparable analogue, to imply “neighboring group participation” of allyl group, that is, promotion of the ring-opening reaction of benzoxazine by stabilizing the resulting cationic species with π-electrons of allyl group intramolecularly.

    12. Synthesis of novel hyperbranched poly(ester-amide)s based on neutral α-amino acids via “AD + CBB′” couple-monomer approach (pages 5364–5374)

      You-Mei Bao, Xiao-Hui Liu, Xiu-Lan Tang and Yue-Sheng Li

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24340

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      Amino acid-based hyperbranched poly(ester-amide)s with numerous hydroxyl end groups were prepared via the “AD + CBB′” couple-monomer technique benefited from advantages of thiol-ene chemistry. The ABB′ intermediates were created through thio-Michael addition reaction near quantitatively in the presence of catalytic amount of Et3N at ambient temperature. In situ self-polycondensation of the ABB′ species with catalyst gave hyperbranched polymers with moderately high molecular weights and degrees of branching

    13. Stimuli-responsive polymer hydrogels containing partially exfoliated graphite (pages 5375–5381)

      Valeria Alzari, Alberto Mariani, Orietta Monticelli, Luca Valentini, Daniele Nuvoli, Massimo Piccinini, Sergio Scognamillo, Silvia Bittolo Bon and Javier Illescas

      Article first published online: 1 OCT 2010 | DOI: 10.1002/pola.24341

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      Frontal polymerization was used for the preparation of a stimuli-responsive composite polymer hydrogel containing partially exfoliated graphite. The maximum temperature reached by the polymerization front and the lower critical solution temperature have been found to be affected by the graphite content.

    14. Dispersion polymerization accompanied by CO2 fixation: Synthesis of particles of polymers bearing cyclic carbonate and epoxide moieties (pages 5382–5390)

      Bungo Ochiai and Takahiro Nakayama

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24342

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      Radical dispersion polymerization of glycidyl methacrylate accompanied by CO2 fixation yielded particles of polymers bearing cyclic carbonate and epoxide moieties in the presence of cellulose acetate as a polymeric dispersion stabilizer. Spherical particles with diameters of 1–10 μm could be prepared under the optimized conditions. The epoxide moieties in the particle were hydrolyzed selectively keeping the shapes of the particles.

    15. Synthesis and properties of novel phosphorus-containing thermotropic liquid crystalline copoly(ester imide)s (pages 5391–5403)

      Diana Serbezeanu, Tachita Vlad-Bubulac, Corneliu Hamciuc and Magdalena Aflori

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24344

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      A comprehensive study on the synthesis and on the relationship between the aliphatic/aromatic ratio, polymer liquid crystalline phase structure, and thermooxidative stability of a series of TLC aromatic–aliphatic copoly(ester imide)s derived from various ratios of a new monomer, namely 1,4-bis[N-(4-hydroxyphenyl)phthalimidyl-5-carboxylate]-2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-naphtalene, various aliphatic diols, and terephthaloyl bis-(4-oxybenzoyl-chloride) is presented.

    16. Synthesis of amphiphilic block copolymers bearing stable nitroxyl radicals (pages 5404–5410)

      Xiuli Zhuang, Chunsheng Xiao, Kenichi Oyaizu, Natsuru Chikushi, Xuesi Chen and Hiroyuki Nishide

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24345

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      A diblock copolymer MPEG-b-PTAm and a triblock copolymer MPEG-b-PLA-b-PTAm containing stable TEMPO free radicals were synthesized by RAFT polymerization followed by oxidation of the precursor polymers. The obtained block copolymers could self-assemble into micellar structure with free radicals in the core, generating stable EPR signal in aqueous solution even in the presence of high concentration of reducing reagent. Combining with the biocompatibility, these materials would show promising use as EPR probes for bioimaging in vivo.

    17. Optically active polyacrylamides bearing an oxazoline pendant: Influence of stereoregularity on both chiroptical properties and chiral recognition (pages 5411–5418)

      Wei Lu, Liping Lou, Fangyu Hu, LiMing Jiang and Zhiquan Shen

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24346

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      The stereospecific radical polymerization of acrylamide derivatives bearing a chiral oxazoline chromophore ((S)-MeOPAM) and (S)-PriOPAM) was achievable in the presence of rare earth metal trifluoromethanesulfonates using n-butanol as solvent. The chiroptical and fluorescence properties of resultant polymers were significantly dependent on the main chain stereoregularity. 1H NMR investigations have proved the enantioselective interaction of the optically active polymers with 1,1′-bi-2-naphthol, in which the characteristic hydroxyl proton signal was split into two peaks that ascribed respectively to the levo- and dextro-isomer. The chiral discrimination ability of the polymers was positively proportional to their diad isotacticity.

    18. Synthesis and characterization of fluorine-containing PAA-b-PTPFCBPMA amphiphilic block copolymer (pages 5419–5429)

      Yongjun Li, Sen Zhang, Hao Liu, Qingnuan Li, Wenxin Li and Xiaoyu Huang

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24347

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      A series of fluorine-containing PAA-b-PTPFCBPMA amphiphilic block copolymer was synthesized via sequential ATRP of tBA and p-(2-(p-tolyloxy)perfluorocyclobutoxy)phenyl methacrylate followed by selective acidic hydrolysis of PtBA block.

    19. One-pot preparation of ABA-type block-graft copolymers via a combination of “click” chemistry with atom transfer nitroxide radical coupling reaction (pages 5430–5438)

      Rongkuan Jing, Guowei Wang and Junlian Huang

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24349

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      Preparation of ABA-type block-graft copolymer was conducted via a combination of CuAAC “Click” chemistry and ATNRC reaction in one pot. The Cu0 added in the one-pot reaction could improve the efficiency of NRC reaction.

    20. Copper(0)-mediated living radical polymerization of acrylonitrile: SET-LRP or AGET-ATRP (pages 5439–5445)

      Xiao-Hui Liu, Gui-Bao Zhang, Bai-Xiang Li, Yun-Gang Bai and Yue-Sheng Li

      Article first published online: 7 OCT 2010 | DOI: 10.1002/pola.24350

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      Copper(0)-mediated living radical polymerization was first applied to synthesize polyacrylonitrile with a high molecular weight and a low polydispersity index. UV-vis spectroscopic analyses indicate that the polymerization mechanism belongs to SET-LRP rather than AGET ATRP.

    21. Reversible addition-fragmentation chain transfer polymerization of a typical hydrophobic monomer of styrene within microreactor of shell-corona hollow microspheres suspending in water (pages 5446–5455)

      Minchao Zhang and Wangqing Zhang

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24351

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      RAFT polymerization of a typical hydrophobic monomer of styrene within microreactor of shell-corona hollow microspheres of poly(styrene-co-methacrylic acid) suspending in water is studied. This RAFT polymerization contains the procedures of encapsulation of the monomer mixture, RAFT polymerization within the microreactor, and release of the polymer. It is found that the resultant polymer of polystyrene has a competitively low polydispersity index and its number-average molecular weight linearly increases with monomer conversion. The method is believed to be a new strategy of RAFT polymerization of hydrophobic monomer in aqueous solution.

    22. Surface morphology and amide concentration depth profile of aminolyzed poly(ethylene terephthalate) films (pages 5456–5467)

      Mihaela Avadanei, Mioara Drobota, Iuliana Stoica, Elena Rusu and Virgil Barboiu

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24354

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      The surface morphology of oriented polyethylene terephthalate films could be changed when they are immersed in hot triethylenetetramine, and the corresponding depth profiles of amide concentration is obtained by means of variable angle attenuated total reflection fourier transform infrared spectra. Similar data are presented and discussed for other two amines, ethylenediamine and tetraethylenepentamine.

    23. Novel poly(ethylene glycol) monomers bearing diverse functional groups (pages 5468–5478)

      Dana M. Mizrahi, Melany Omer-Mizrahi, Jenny Goldshtein, Nataly Askinadze and Shlomo Margel

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24355

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      Novel functional PEG monomers were prepared, bearing important functional groups, such as carboxylic acid, amine and thiol. These monomers are suitable for preparation of functionalized particles and coatings. Moreover, they may be used to form multibioconjugates. Full synthetic details, and initial polymerization studies, are reported.

    24. Synthesis and applications of 2,7-carbazole-based conjugated main-chain copolymers containing electron deficient bithiazole units for organic solar cells (pages 5479–5489)

      Dhananjaya Patra, Duryodhan Sahu, Harihara Padhy, Dhananjay Kekuda, Chih-Wei Chu and Hong-Cheu Lin

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24356

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      A series of conjugated main-chain copolymers (P1P4) consisting of 2,7-carbazole electron-donating unit and bithiazole electron-accepting unit were synthesized and investigated for the bulk heterojunction solar cell applications. Polymer P4 produced the highest power conversion efficiency value of 1.01% fabricated with a device structure of ITO/PEDOT:PSS/P4:PC71BM (1:1.5, w/w)/Ca/Al measured under 100 mW/cm2 of AM 1.5 white-light illumination.

    25. A convenient route to PHB macromonomers via anionically controlled moderate-temperature degradation of PHB (pages 5490–5497)

      Michał kawalec, Michał Sobota, Mariastella Scandola, Marek Kowalczuk and Piotr Kurcok

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24357

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      1H NMR spectra in range of methyl group protons of acetate chain end (incorporated acetate initiator) and acetic acid as well as methyl group protons of crotonate chain ends and crotonic acid(s) of atactic PHB/salt nonvolatile degradation products after 4.5 h at 150 °C. Alkali metal salts are shown to be the most effective compounds for the rapid and controlled degradation of PHBs in relatively mild conditions. An efficient method for obtaining valuable, low molar mass PHBs macromonomers via reactive blending has been developed.

    26. Synthesis and nonlinear optical properties of polyacetylenes containing oxadiazole and thiophene pendant groups with high thermal stability (pages 5498–5504)

      Xin Wang, Yongxin Yan, Tianbao Liu, Xinyan Su, Liwu Qian, Yinglin Song and Hongyao Xu

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24358

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      The functional polyacetylene by incorporating both thiophene and oxadiazole into polyacetylene effectively enhances thermal stability because of the synergetic effect of the “jacket effect” and the effect of retarding or eliminating thermally induced transformations, meanwhile large nonlinear optical susceptibility was obtained.

    27. Thiol-terminated polyisobutylene: Synthesis, characterization, and derivatization (pages 5505–5513)

      Andrew J. D. Magenau, Todd R. Hartlage and Robson F. Storey

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24359

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      Thiol-terminated polyisobutylene (α,ω-PIB-SH) was synthesized from thiourea and α,ω-bromine-terminated PIB in a cosolvent system of 1:1 (v:v) heptane:dimethylformamide. Basic hydrolysis of the intermediate alkylisothiouronium salt at 110 °C resulted in thiolate chain ends, which were re-acidified to form telechelic PIB-SH. Alkyne-terminated PIB was synthesized from PIB-SH by a phosphine-catalyzed thiol-ene Michael addition with propargyl acrylate. Extending this reaction produced tetra-hydroxy functionalized PIB by a sequential thiol-ene/thiol-yne procedure. Base-catalyzed thiol-isocyanate reactions were used to produce PIB based thiourethanes with and without a small-molecule chain extender. Increased molecular weights and thiol group conversion were observed with GPC and 1H NMR, respectively.

    28. Synthesis of three new 1-(2,6-diisopropylphenyl)-2,5-di(2-thienyl) pyrrole-based donor polymers and their bulk heterojunction solar cell applications (pages 5514–5521)

      Vellaiappillai Tamilavan, Myungkwan Song, Sung-Ho Jin and Myung Ho Hyun

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24360

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      New 1-(2,6-diisopropylphenyl)-2,5-di(2-thienyl)pyrrole homopolymer and copolymers containing 2,5-dioctyloxyphenylene and 3-octylthiophene were prepared and applied for bulk heterojunction solar cells.

    29. Telechelic polynorbornenes with hydrogen bonding moieties by direct end capping of living chains (pages 5522–5532)

      Steffen Kurzhals and Wolfgang H. Binder

      Article first published online: 15 OCT 2010 | DOI: 10.1002/pola.24362

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      Internal olefins bearing hydrogen bonding moieties (barbiturate and thymine) were synthesized and applied for the direct end capping of living chains, prepared via ROMP. Characterization of the polymers and the determination of the quenching efficiency were accomplished via MALDI-TOF MS.

    30. Characterization of different poly(2-oxazoline) block copolymers by MALDI-TOF MS/MS and ESI-Q-TOF MS/MS (pages 5533–5540)

      Anja Baumgaertel, Esra Altuntaş, Kristian Kempe, Anna Crecelius and Ulrich S. Schubert

      Article first published online: 15 OCT 2010 | DOI: 10.1002/pola.24364

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      Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry coupled with a collision-induced dissociation (CID) unit (MALDI-TOF MS/MS) and electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-Q-TOF MS/MS) were chosen to prove the fragmentation behavior of block copolymers under high energy conditions. A variety of possible fragmentation mechanisms, like McLafferty+1 rearrangement, could be found for both characterization techniques.

    31. Functionalization of multiwalled carbon nanotubes with polyesters via bergman cyclization and “grafting from” strategy (pages 5541–5548)

      Jianguo Ma, Xin Cheng, Xiaowei Ma, Sheng Deng and Aiguo Hu

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24365

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      Polyesters-grafted MWNTs were synthesized through Bergman cyclization followed by ring-opening polymerization of ε-caprolactone and lactide. A variety of techniques such as TGA, NMR, TEM, UV-vis, TEM, and Raman spectroscopy were used to characterize surface functionalities. Fabrication of MWNTs polymer nanocomposites was revealed through electrospinning.

    32. Synthesis of end-functionalized poly(phenylacetylene)s with well-characterized palladium catalysts (pages 5549–5556)

      Masashi Shiotsuki, Atsushi Nakagawa, Jesus Rodriguez Castañon, Naoya Onishi, Tatsurou Kobayashi, Fumio Sanda and Toshio Masuda

      Article first published online: 15 OCT 2010 | DOI: 10.1002/pola.24366

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      End-functionalized poly(phenylacetylene)s were synthesized by the polymerization of phenylacetylene (PA) using the well-defined palladium catalysts represented as [(dppf)PdBr(R)] (dppf = 1,1′-bis(diphenylphosphino)ferrocene). The obtained poly(PA) bearing a hydroxy end group was applied as a macroinitiator to the synthesis of a block copolymer composed of poly(PA) and poly(β-propiolactone) moieties.

    33. The improvement of electro-optical properties of polymer-dispersed liquid crystals using copolymer macroinitiator with different glass transition temperature (pages 5557–5561)

      Xin Du, Bin Yan, Jiali Yao, Shu Chen, Minke Li and Yinghan Wang

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24367

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      In this article, we found that the copolymer macroinitiator of styrene and iso-octyl acrylate (prepared by Reversible Additional-Fragmental chain Transfer (RAFT) polymerization) can be used to prepare PDLCs with both low driving voltage and low memory effect. The appropriate Tg of the macroinitiators was the key reason for the low memory effect in resulted PDLCs.

    34. Synthesis and characterization of soluble conjugated polymers having pyrene moiety in the main chain (pages 5562–5569)

      Hui Chen, Xiao Hu and Siu-Choon Ng

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24369

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      Soluble alternating conjugated polymers consisting of pyrene and thiophene/fluorene moieties have been successfully prepared using Suzuki coupling reaction. Thermal and electrochemical studies indicated that the polymers have good thermal stability as well as good oxidative stability. These conjugated polymers showed efficient blue light-emitting properties and are expected to be promising candidates for pure blue light emitting device applications.

    35. Novel superhydrophobic silica/poly(siloxane-fluoroacrylate) hybrid nanoparticles prepared via two-step surface-initiated ATRP: Synthesis, characterization, and wettability (pages 5570–5580)

      Hai-Jiang Yu and Zheng-Hong Luo

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24371

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      Novel superhydrophobic silica/poly(siloxane-fluoroacrylate) hybrid nanoparticles were prepared by two-step surface-initiated ATRP. It is revealed that the surfaces of the nanoparticles are rough at the microscale and nanoscale. With the increase of HFBMA conversion, the surface roughness of the SiO2/PMPTS-b-PHFBMA films increases gradually, which results in a series of WCAs ranging from 135° to 161°. The combination of surface chemistry and roughness of the hybrid nanoparticles leads to the super water repellency.

    36. Mass spectrometry characterization of 3-OH butyrated β-cyclodextrin (pages 5581–5592)

      Cristian Peptu, Alina Nicolescu, Catalina A. Peptu, Valeria Harabagiu, Bogdan C. Simionescu and Marek Kowalczuk

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24372

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      Oligo(3-OH butyrate)-β-cyclodextrin esters (PHB-CD) were obtained through ring opening of β-butyrolactone (β-BL) in the presence of β-cyclodextrin (CD) and (-)-sparteine (SP) as nucleophilic activator. Mass spectrometry characterization revealed that poly(3-OH butyrate) homopolymers (PHB-A) and crotonic acid-ended PHB (PHB-B) (F1 fraction) are formed together with the PHB-CD products (F2 fraction).

    37. Radical polymerization of styrene derivatives bearing N-free amino acid side chains, synergic effect of chirality, and hydrogen bonding for stereoselective polymerization (pages 5593–5602)

      Kouki Matsubara, Atsumi Kurimaru, Miyuki Yamanaka, Tetsuya Hirashima, Yoshie Onishi, Eiji Murakami, Emi Kawachi, Yuji Koga and Setsuko Ando

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24274

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      Radical polymerization of styrene derivatives having a series of amino acid was conducted to regulate the stereoinduction system. Isotacticity increased in the polymer main chain, especially in the polymerization of monomers bearing N-free (L)-leucine and (L)-valine in THF or DMF at 50 °C, by the synergic stereoregulation with chirality control and hydrogen bonding between the polymer radical terminal and the monomer.

    38. Electrochemical and optical studies of furan and thieno[3,2-b]thiophene end capped benzotriazole derivatives (pages 5603–5610)

      Naime Akbaşoğlu, Abidin Balan, Derya Baran, Ali Cirpan and Levent Toppare

      Article first published online: 15 OCT 2010 | DOI: 10.1002/pola.24375

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      Two DAD type polymers were synthesized electrochemically from furan or thieno[3,2-b]thiophene (TT) end-capped benzotriazole monomers. Cyclic Voltammetry (CV) and spectroelectrochemistry studies showed that both conjugated polymers are multicolored electrochromic polymers. Results and comparison with properties of other benzotriazole based DAD type polymers are highlighted.

    39. Optically active composite nanoparticles with chemical bonds between core and shell (pages 5611–5617)

      Xiaofeng Luo, Xiaoqing Liu, Bo Chen, Jianping Deng and Wantai Yang

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24376

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      Optically active core/shell nanoparticles consisting of a core of helical polyacetylenes and a shell of vinyl polymer were prepared via catalytic polymerization (first stage) in the presence of Rh catalyst and free radical polymerization (second stage) without additional initiator. The helical conformation of the polyacetylenes in the core/shell nanoparticles had high thermal stability due to the protection of the shell.

    40. Synthesis and characterization of poly(methylmethacrylate)/silica nanocomposites: Study of the interphase by solid-state NMR and structure/properties relationships (pages 5618–5629)

      Roberto Avolio, Gennaro Gentile, Maurizio Avella, Donatella Capitani and Maria Emanuela Errico

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24377

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      An effective compatibilization route was set up to realize PMMA based nanocomposites containing silica nanoparticles. Solid state NMR spectroscopy was a very powerful tool to probe the nature of interactions established between organic and inorganic phase and to clarify the reaction mechanism involving organic groups introduced onto silica and the growing acrylic macroradicals during the in situ polymerization of polymer matrix (PMMA). As a result of these interactions the formation of an interphase consisting of PMMA chains grafted onto the silica surface was obtained, responsible for a strong polymer/nanophase interfacial adhesion as well as significant improvements of nanocomposite physical properties.

  2. Rapid Communications

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    1. Aggregation of ε-caprolactone polymers containing at one chain end different number of carboxyl groups in the presence of calcium cations (pages 5630–5635)

      Melania Bednarek, Tadeusz Biedroń and Przemysław Kubisa

      Article first published online: 5 OCT 2010 | DOI: 10.1002/pola.24353

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      The aggregation of poly(ε-caprolactone) containing different number of carboxyl groups at one chain end in the presence of Ca2+ cations was investigated by viscosity measurements. With increasing number of carboxyl groups, aggregation is strongly enhanced as evidenced by the viscosity-time profiles. The formation of long cylindrical structures was observed by scanning electron microscopy.

  3. Notes

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    1. You have free access to this content
      Nitroxide-mediated radical polymerization of carbon dioxide-expanded methyl methacrylate (pages 5636–5641)

      Da Wei Pu, Frank P. Lucien and Per B. Zetterlund

      Article first published online: 13 OCT 2010 | DOI: 10.1002/pola.24343

      Thumbnail image of graphical abstract

      Nitroxide-mediated radical polymerization based on TEMPO has been performed for methyl methacrylate under conditions of CO2-expanded monomer at 7 MPa and 90°C. The fraction of propagating radicals lost due to disproportionation with nitroxide, a well-known problem in NMP of methacrylates, decreased in the presence of CO2. This is consistent with deactivation between propagating radical and nitroxide proceeding more rapidly in the lower viscosity induced by CO2. However, the polymerization ceased at relatively low conversions of approximately 19% both with and without CO2, indicating that disproportionation between propagating radical and nitroxide is a major problem also in CO2-expanded MMA.

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