Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

1 September 2010

Volume 48, Issue 17

Pages 3709–3912

  1. Articles

    1. Top of page
    2. Articles
    1. Catalytic synthesis of styryl-capped isotactic polypropylenes (pages 3709–3713)

      Huahua Huang, Chengang Cao, Hui Niu and Jin-Yong Dong

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24139

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      A new chain transfer mechanism was derived in propylene polymerization with rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride-methylaluminoxane in the presence of 1,4-divinylbenzene (DVB) or 1,2-bis(4-vinylphenyl)ethane (BVPE) together with hydrogen (H2). The chain transfer reaction takes place in a unique way where, prior to the ultimate chain transfer leading to the formation of a terminal styryl group, DVB and BVPE act as a comonomer forming main chain benzene rings. This bis-styrenic molecule/H2 chain transfer approach makes a convenient way to accessing terminally reactive/functional i-PP.

    2. Anionic polymerization of N,N-dialkyl-2-methylenebut-3-enamide: Effect of alkyl substituents on polymerization behavior (pages 3714–3721)

      Katsuhiko Takenaka, Natsuyo Shibata, Akihiko Oshikiri, Masamitsu Miya, Hiroki Takeshita and Tomoo Shiomi

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24146

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      Anionic polymerizations of three 1,3-butadiene derivatives containing different N,N-dialkyl amide functions were performed under various conditions, and their polymerization behavior and microstructure of the resulting polymers were found to strongly depend on the structure of N-alkyl substituents.

    3. Preparation of bimodal HDPEs with metallocene on Cr-montmorillonite support (pages 3722–3728)

      Kazuhiro Yamamoto, Yoshiyuki Ishihama and Kazuya Sakata

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24154

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      Previously described Cr-montmorillonite (Cr-MMT) was found to retain reactivity in the ethylene polymerization reaction regardless of which alkyl-metal was used for workup in the preparation process, as long as alkylaluminium was used as a co-catalyst in the actual polymerization reaction. Introduction of hydrogen pressure was found to regulate the polymerization to give the product polymer with a narrower weight distribution, albeit with a somewhat smaller average molecular weight. Supporting metallocene onto Cr-MMT produced a binuclear catalyst system which gave rise to bimodal polyethylene (PE). Polymer composition of the produced HDPEs could be controlled by changing factors such as the polymerization conditions and the identity of the metallocene compounds.

    4. Synthesis and characterization of nitrogen-linked carbazole-containing fluorescent polymers (pages 3729–3735)

      Koji Takagi, Hidenobu Takao and Tsuyoshi Nakagawa

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24155

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      Four nitrogen-linked carbazole-containing fluorescent polymers were synthesized by the Suzuki coupling polycondensation. From the UV and PL spectra of polymers having the insulating p-xylylene spacer, the influence of a chromophore composed of carbazole and fluorene on optical properties was investigated. On the other hand, polymers having the heterocycle directly bound to the carbazole nitrogen were designed to know the character of the carbazole nitrogen lone pair and their influence on the fluorescence behavior.

    5. Controlled cationic polymerization of styrene using AlCl3OBu2 as a coinitiator: Toward high molecular weight polystyrenes at elevated temperatures (pages 3736–3743)

      Alexander N. Frolov, Sergei V. Kostjuk, Irina V. Vasilenko and Fyodor N. Kaputsky

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24158

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      An efficient AlCl3-based initiating system, CumOH/AlCl3OBu2/Py, for the controlled cationic polymerization of styrene at low [AlCl3OBu2]/[CumOH] ratio (2–4) and elevated temperatures (–40…–60 °C) was proposed. Polystyrenes with the molecular weight as high as 85,000 g mol−1 and reasonable MWD (Mw/Mn = 1.8–2.0) could be prepared under these conditions. The propagation reaction order was found to be 1 with respect to Lewis acid coinitiator while the apparent activation energy was found high and positive (Ea,app = 60.9 kJ mol−1).

    6. Synthesis and luminescence of poly(phenylacetylene)s with pendant iridium complexes and carbazole groups (pages 3744–3757)

      José Vicente, Juan Gil-Rubio, Guijiang Zhou, Henk J. Bolink and Joaquín Arias-Pardilla

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24159

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      Organometallic poly(phenylacetylene)s containing different amounts of carbazole, and iridium emitters attached to the main chain have been synthesized by Rhodium-catalyzed copolymerization of phenylacetylenes containing pendant iridium complexes and 9-(4-ethynylphenyl)carbazole. Their electrochemical and photophysical properties have been studied. The films made from polymers of the phenylisoquinoline series display iridium-based phosphorescence and electroluminescence.

    7. Synthesis and characterization of functionalized water soluble cationic poly(ester amide)s (pages 3758–3766)

      Xuan Pang, Jun Wu, Cynthia Reinhart-King and Chih-Chang Chu

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24160

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      A new family of positively charged, water soluble, and functional amino acid-based poly(ester amide)s (Arg-AG PEA) were synthesized by the solution copolycondensation. Functional pendant carbon–carbon double bonds located in the DL-2-allylglycine unit were incorporated into these Arg-AG PEAs. The cytotoxity of Arg-AG PEAs was evaluated by MTT assay. These preliminary MTT results indicated that Arg-AG PEAs were nontoxic to bovine aortic endothelial cells (BAECs).

    8. Hydrolytic degradation of polyisobutylene and poly-L-lactide–based multiblock copolymers (pages 3767–3774)

      Umaprasana Ojha, Pallavi Kulkarni, David Cozzens and Rudolf Faust

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24161

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      The hydrolytic degradation of a series of poly-L-lactide (PLLA) and polyisobutylene (PIB)–based multiblock copolymers was studied. The degradation rate was strongly dependent on the PLLA segment length and wt % in the polymer.

    9. Synthesis and application of molybdenum (III) complexes bearing weakly coordinating anions as catalysts of isobutylene polymerization (pages 3775–3786)

      Bernd E. Diebl, Yang Li, Mirza Cokoja, Fritz E. Kühn, Narayanan Radhakrishnan, Stefan Zschoche, Hartmut Komber, Hui Yee Yeong, Brigitte Voit, Oskar Nuyken, Phillip Hanefeld and Hans-Michael Walter

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24162

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      Acetonitrile ligated molybdenum (III) complexes of the structure [MoCl(NCCH3)5]2+ bearing different weakly coordinating anions [B(C6F5)4], [B{C6H3(m-CF3)2}4] and [(C6F5)3B-C3H3N2-B(C6F5)3] were applied as homogeneous catalysts of the polymerization of isobutylene. Highly reactive low molecular weight polyisobutylenes (Mn < 2000 g/mol) were obtained with a high content of exo double bond end groups as shown by 1H NMR analysis.

    10. Development of reactive methacrylates based on glycidyl methacrylate (pages 3787–3796)

      Ozlem Karahan, Kinyas Aydin, Seda Edizer, Nihan Odabasi and Duygu Avci

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24163

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      Six methacrylate monomers based on glycidyl methacrylate have been synthesized for use as reactive diluents in dental composites. The monomers showed high cross-linking tendencies during thermal bulk polymerizations. The photopolymerization rate of monomers 26 were found to be greater than TEGDMA, Bis-GMA, HEMA, and GDMA. Low sensitivity of the monomers to oxygen is consistent with the crosslinked polymer formation due to a proposed hydrogen abstraction chain transfer reaction. The computationally calculated dipole moment and LUMO energies indicated that there seems to be a correlation between these quantities and reactivity for ester linked monomers.

    11. Investigation of thiol-ene addition reaction on poly(isoprene) under UV irradiation: Synthesis of graft copolymers with “V”-shaped side chains (pages 3797–3806)

      Guowei Wang, Xiaoshan Fan and Junlian Huang

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24164

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      Poly(isoprene) (PI) with pendant functional groups was successfully synthesized by thiol-ene addition reaction under UV irradiation, and the results showed that the addition reaction only occurred at double bonds corresponding to 1,2-addition of isoprene units, as well as the groups density could be easily controlled by variation of the contents of modified 1,2-addition isoprene units on PI. PI main chain could be further modified and used to prepare graft copolymers PI-g-PS2 and PI-g-PtBA2 and the following PI-g-PAA2. Our work provided a versatile strategy to the graft copolymers with poly(diene) as main chain, and the these copolymers might be used as a kind of novel materials.

    12. Ring-opening polymerization of 1-methyltrimethylene carbonate by rare earth initiators (pages 3807–3815)

      Jun Ling, Yongbo Dai, Yinghong Zhu, Weilin Sun and Zhiquan Shen

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24166

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      Controlled ring-opening polymerizations of 1-methyltrimethylene carbonate (MTMC) were initiated by single-component rare earth compounds at mild conditions. The “coordination-insertion” mechanism was confirmed by both experimental and theoretical studies. MTMC rings were opened via acyl-oxygen bond cleavages in which mode b was the major pathway.

    13. Synthesis of an amphiphilic polymer having hydrophobic acetal and hydrophilic pyrrolidone moieties and its application to persisting release of aldehyde as a pro-fragrance (pages 3816–3822)

      Yanmei Wang, Hisatoyo Morinaga, Atsushi Sudo and Takeshi Endo

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24167

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      A new amphiphilic polymer having octanal-derived acetal moieties was synthesized from poly(vinyl alcohol-co-N-vinyl pyrrolidone). The polymer released octanal by hydrolysis of the acetal side chain under acidic conditions. The release of octanal was enhanced by the increased hydrophilicity of the polymer due to the presence of pyrrolidone moiety.

    14. Chemical modification of the pendant structure of wholly aromatic polyamides: Toward functional high-performance materials with tuned chromogenic and fluorogenic behavior (pages 3823–3833)

      Pedro Estévez, Hamid El-Kaoutit, Félix Clemente García, Felipe Serna, José Luis de la Peña and José Miguel García

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24168

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      The chemical modification of aromatic polyamides with pendant fluorescent groups permits the design of high-performance materials with “a la carte” fluorescence and chromogenic behavior, valid for novel technological applications, that is, luminescent converter materials for hybrid light-emitting diode applications or for the preparation of selective chromogenic and fluorogenic sensing materials in sensing devices.

    15. Cleavage of polystyrene-b-poly(ethylene oxide) block copolymers with a trithiocarbonate linkage in solutions (pages 3834–3840)

      Min Cao, Jian-Qi Wang, Peng-Cheng Chen, Jun-Ting Xu and Zhi-Qiang Fan

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24169

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      Polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymers with a trithiocarbonate group as the junction were prepared. Cleavage of the trithiocarbonate group by UV irradiation in common solvent or selective solvents was investigated. The cleavage ratio ranges from 76 to 86% and the size of the micelles is reduced after cleavage.

    16. Synthesis of Poly(3,4-ethylenedioxythiophene) latexes using poly(N-vinylpyrrolidone)-based copolymers as reactive stabilizers (pages 3841–3855)

      Muhammad Mumtaz, Christine Labrugère, Eric Cloutet and Henri Cramail

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24171

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      Poly(3,4-ethylenedioxythiophene) (PEDOT) nano-objects with homogeneous size distribution have been synthesized using ammonium persulfate as an oxidant in the presence of poly(N-vinylpyrrolidone)-based block and statistical copolymer reactive stabilizers in aqueous media. These PEDOT nano-objects show conductivities up to 3× 10−4 S/cm despite the presence of insulator material.

    17. Synthesis of heterocyclic monomers via Reissert chemistry (pages 3856–3867)

      Harry W. Gibson, Kimberly K. Brumfield, Roger A. Grisle and Christine K. F. Hermann

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24172

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      The chemistry of Reissert compounds has been used to synthesize activated difluorotetraketone monomers containing two coupled isoquinolyl moieties, linked at either the 1,1′- or 4,4′-positions. These monomers offer routes to novel families of poly(heteroarylene ether)s. The example below illustrates preparation of a bis(Reissert compound) from a 4,4′-coupled bisisoquinoline, its conversion to a new difluorotetraketo monomer, and its incorporation into a new polymer. Two 1,1′-linked bisisoquinoline difluoroketo monomers prepared analogously via Reissert compound chemistry are also shown.

    18. Highly efficient and stable blue-light-emitting binaphthol-fluorene copolymers: A joint experimental and theoretical study of the main-chain chirality (pages 3868–3879)

      Zhongfu An, Jun Yin, Naien Shi, Hongji Jiang, Runfeng Chen, Huifang Shi and Wei Huang

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24173

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      A series of soluble conjugated main-chain chiral copolymers (PF-BNs) derived from fluorene and axially chiral 1,1′-binaphthol (BINOL) were successfully prepared. The copolymers with proper content of BINOL show highly efficient and ultra highly stable blue light-emission with almost unchanged fluorescent spectra after annealing at 200 °C in air for 10 h. The joint experimental and theoretical study reveals that the effective conjugation length of PF-BNs is about one BINOL and three fluorenes, whereas the chirality of BINOL can be transferred to the polymer backbone and the main active chiral block in copolymers is probably composed by one BINOL with two or three fluorenes.

    19. Construction of hydroxyl-terminated poly(N-isopropylacrylamide) brushes on silicon wafer via surface-initiated atom transfer radical polymerization (pages 3880–3887)

      Eylem Turan and Tuncer Caykara

      Version of Record online: 16 JUL 2010 | DOI: 10.1002/pola.24170

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      Poly(N-isopropylacrylamide) poly(NIPAM) brushes with hydroxyl end-group on silicon wafer surface were prepared by combining the self-assembled monolayer of initiator and atom transfer radical polymerization in the presence of 2-mercaptoethanol (ME) chain transfer agent. The results of grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, atomic force microscopy, gel permeation chromatography, and water contact-angle measurements confirmed the formation of homogeneous tethered poly(NIPAM) brushes with hydroxyl end-group.

    20. Photo-crosslinked fluorinated thin films from azido-functionalized random copolymers (pages 3888–3895)

      Samer Al Akhrass, Denis Damiron, Géraldine Carrot and Eric Drockenmuller

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24175

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      Thermally and chemically stable fluorinated coatings are obtained from the photo-crosslinking of fluorinated azido-functionalized random copolymers thin films. Such coatings can easily and accurately control the surface properties of a wide range of organic and inorganic coatings.

    21. Synthesis of a norbornene monomer having cyclic carbonate moiety based on CO2 fixation and its transition metal-catalyzed polymerizations (pages 3896–3902)

      Atsushi Sudo, Hidetada Morishita and Takeshi Endo

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24176

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      A norbornene monomer bearing cyclic carbonate moiety (NB-CC) was synthesized from the corresponding precursor bearing epoxy moiety by its reaction with carbon dioxide under atmospheric pressure. NB-CC underwent the ring-opening metathesis polymerization and the palladium-catalyzed copolymerization with 5-butyl-2-norbornene to afford the corresponding poly(norbornene)s having cyclic carbonate moiety in the side chain.

    22. A versatile surfactant-mediated synthetic route to gold/polyaniline derivative core/shell nanocomposites (pages 3903–3912)

      Jie Han, Yan Liu, Lu Wang and Rong Guo

      Version of Record online: 15 JUL 2010 | DOI: 10.1002/pola.24177

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      Well-defined gold/poly(o-toluidine) core/shell nanocomposites have been successfully fabricated with the aid of surfactant F127. Mechanistic studies reveal that surfactant concentration lower than CMC is crucial for successful synthesis of uniform core/shell nanocomposites. Tunable shell thickness can be realized by controlling reaction time or monomer concentration. Size of gold colloid can be altered in a wide range but limited to several nanometers. Extension of this approach to other gold/polyaniline derivative core/shell nanocomposites, such as gold/poly(o-aminothiophnol) or gold/poly(o-phenylenediamine) core/shell nanocomposites are also successful, indicating the versatility of our proposed method for gold/polymer core/shell nanocomposites.