Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 16

15 August 2006

Volume 44, Issue 16

Pages 4709–4938

  1. Articles

    1. Top of page
    2. Articles
    3. Notes
    1. Relationship between the liquid crystallinity and field-effect-transistor behavior of fluorene–thiophene-based conjugated copolymers (pages 4709–4721)

      Eunhee Lim, Young Mi Kim, Jeong-Ik Lee, Byung-Jun Jung, Nam Sung Cho, Jaemin Lee, Lee-Mi Do and Hong-Ku Shim

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21586

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      A series of fluorene–thiophene-based copolymers was synthesized through a palladium-catalyzed Suzuki coupling reaction. The copolymers were designed to possess polar oxaheptyl side chains, the dimer of the fused thiophene, or a hole-transporting unit. The physical and optical properties of the polymers were carefully characterized. Studies of the differential scanning calorimetry and field-effect transistors (FET) revealed that more crystalline polymers gave better FET device performance. With this study, we could assess the liquid-crystallinity dependence of the field-effect carrier mobility on organic FETs based on liquid-crystalline copolymers.

    2. Microwave-assisted synthesis of a novel phosphorus-containing spiroorthoester, characterization and cationic polymerization (pages 4722–4730)

      J. Canadell, A. Mantecón and V. Cádiz

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21575

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      A new phosphorus-containing spiroorthoester, (1,4,6-trioxaspiro [4,4] nonan-2-yl)-methyl 3-[10-(9,10-dihydro-9-oxa-9-phosphaphenanthrene-10-oxide)]-propanoate, was synthesized under microwave irradiation with a short reaction time. The structure of the new monomer was confirmed by 1H, 13C, and 31P. This phosphorus-containing spiroorthoester was homopolymerized and copolymerized with phenylglycidyl ether with ytterbium triflate as a cationic initiator. These reactions were monitored by FTIR/ATR, and the formation of poly(ether-ester)s with a pendant bulky phosphorylated group was shown.

    3. Polycondensation of α-amino acid esters in the presence of yttrium triflate as a Lewis acid (pages 4731–4735)

      Tadamasa Nemoto, Daisuke Ando, Kensuke Naka and Yoshiki Chujo

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21577

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      To develop polycondensation methods for poly(α-amino acid)s, we describe a first examination to use yttrium triflate as a Lewis acid for polycondensation of α-amino acid esters. In the absence of Lewis acid, no polycondensation of 2-methoxyphenyl glycinate (1b) at room temperature proceeded. While the polycondensation of 1b was carried out with 5 mol % yttrium triflate, a condensation product of glycine was obtained in 16% yield. Although polycondensation of 4-nitrophenyl L-leucinate (1c) and 4-nitrophenyl L-valinate (1d) were also promoted with 5 mol % yttrium triflate, the condensation products of both α-amino acid esters were obtained in only a few percent yield. When 1d was polymerized in the presence of 100 mol % yttrium triflate, high molecular weight poly(L-valine) was obtained in 91% yield.

    4. Acrylic polymer/silica organic–inorganic hybrid emulsions for coating materials: Role of the silane coupling agent (pages 4736–4742)

      Mitsuru Watanabe and Toshiyuki Tamai

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21574

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      Acrylic polymer/silica organic–inorganic hybrid emulsions were synthesized by a simple method, that is, a conventional emulsion polymerization and subsequent sol–gel process, to provide water-based coating materials. The acrylic polymer emulsions contained a silane coupling agent monomer, such as methacryloxypropyltriethoxysilane, to form highly solvent-resistant hybrid films. The films from the hybrid emulsions, which did not have the silane coupling agent monomer in the core part, did not exhibit high solvent resistance. The crosslinked core part and silane coupling agent containing the shell part of the polymer particles played important roles in attaining high solvent resistance.

    5. High-molar-mass polypropene with tunable elastic properties by hafnocene/borate catalysts (pages 4743–4751)

      Tanja Seraidaris, Arto Puranen, Mikko Karesoja, Barbro Löfgren, Timo Repo, Markku Leskelä and Jukka Seppälä

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21571

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      rac- and meso-like Diastereomers Dimethylsilyl(3-benzylindenyl)(2-methylindenyl)hafnium dichloride complexes (Hfr and Hfm, respectively) were synthesized and used as catalyst precursors for the preparation of high-molar-mass polypropenes with moderate isotacticities. By the variation of the polymerization conditions, it was possible to modify the polymer microstructure and molar mass and thereby influence the mechanical properties. The successive self-nucleation and annealing technique revealed that Hfr produced a more uniform material with a narrower distribution of lamellar thicknesses. The dynamic mechanical analysis tests showed comparable creep-recovery properties for the elastic polypropene and the commercial Kraton styrene–(ethene–butene)–styrene block copolymer.

    6. Isomeric effect of the Et(H4Ind)2Zr(CH3)2 catalyst on the copolymerization of ethylene and styrene: A computational study (pages 4752–4761)

      Sonia Martínez, Javier Ramos, Víctor L. Cruz and Javier Martínez-Salazar

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21569

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      Computational calculations based on density functional theory concerning the ethylene–styrene copolymerization process have been carried out with meso-Et(H4Ind)2Zr(CH3)2 as the catalyst. Monomer insertion barriers in this catalyst are evaluated and compared with corresponding values in rac diastereoisomers, which were previously calculated. Some differences in the polymerization activities and also in styrene incorporation are found for both diastereoisomers. The possibility of a retention mechanism during the polymerization process is also studied for the meso-Et(H4Ind)2Zr(CH3)2 catalyst; nevertheless, for both meso and rac diastereoisomers, a migration mechanism seems to be favorable.

    7. Homopolymerization and copolymerization of isocyanatoethyl methacrylate (pages 4762–4768)

      O. A. Lam, Y. Hervaud and B. Boutevin

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21568

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      Isocyanatoethyl methacrylate (IEM) was homopolymerized, and then its copolymerization with methyl methacrylate (MMA) was successfully achieved. Kinetic studies gave reactivity ratios of 0.88 and 1.20 for IEM and MMA, respectively.

    8. Segmented block copolymers based on poly(propylene oxide) and monodisperse polyamide-6,T segments (pages 4769–4781)

      Martijn van der Schuur and Reinoud J. Gaymans

      Article first published online: 14 JUL 2006 | DOI: 10.1002/pola.21587

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      Polyether(ester amide)s with poly(propylene oxide) and monodisperse poly(hexamethylene terephthalamide) segments were synthesized and their structure-property relations investigated. The length of the amide segments was varied from diamide to hexa-amide segments. The poly(propylene oxide) used had a molecular weight of 1000–4000 g/mol. The morphology of the polyether(ester-amide)s was studied with TEM and AFM, the thermal properties with DSC and DMTA and the tensile properties on dumbbell samples. The elastic behavior of the block copolymers was investigated in tensile and compression. The modulus increased strongly with the amide content and this could be described by a fiber composite model.

    9. Complex amphiphilic networks derived from diamine-terminated poly(ethylene glycol) and benzylic chloride-functionalized hyperbranched fluoropolymers (pages 4782–4794)

      Kenya T. Powell, Chong Cheng, Karen L. Wooley, Anuradha Singh and Marek W. Urban

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21576

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      The nucleophilic substitution of diamine terminated poly (ethylene glycol) upon benzylic chlorides within a hyperbranched fluoropolymer afforded crosslinked networks that presented topographically complex and compositionally-heterogeneous surfaces, as measured by atomic force microscopy (top image) and internal reflection infrared imaging (bottom image), respectively.

    10. Synthesis and properties of the polythiourethanes obtained by the cationic ring-opening polymerization of cyclic thiourethanes (pages 4795–4803)

      Daisuke Nagai, Masato Sato, Bungo Ochiai and Takeshi Endo

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21557

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      The cationic ring-opening polymerization of a five-membered cyclic thiourethane [3-benzyl-1,3-oxazolidine-2-thione (BOT)] with boron trifluoride etherate afforded the corresponding poly(thiourethane)s with controlled molecular weights and narrow molecular weight distributions. These results, along with the successful results in the two-stage polymerization, supported the idea that this polymerization would proceed in a controlled manner. The block copolymerizations of BOT with a six-membered thiourethane [3-benzyltetrahydro-1,3-oxazolidine-2-thione (BTOT)] were also carried out to afford the corresponding di- and triblock copolymers. The order of the 5% weight loss temperatures was as follows: poly(3-benzyltetrahydro-1,3-oxazolidine-2-thione) [poly(BTOT)] > poly (BTOT54-b-BOT46) > poly(3-benzyl-1,3-oxazolidine-2-thione) [poly(BOT)] [poly(BOT)]. This indicated that the increase in the BTOT unit content raised the decomposition temperature. The order of the refractive indices was poly(BOT) > poly (BTOT54-b-BOT46) > poly(BTOT54-b-BOT46-b-BTOT50) > poly (BTOT); this was in accord with the order of the sulfur content in the polymer chain.

    11. Synthesis and light-emitting properties of platinum-containing oligoynes and polyynes derived from oligo(fluorenyleneethynylenesilylene)s (pages 4804–4824)

      Wai-Yeung Wong, Suk-Yue Poon, Jian-Xin Shi and Kok-Wai Cheah

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21588

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      New photoluminescent platinum(II)-coordinated oligoynes and polyynes containing a series of oligo(fluorenyleneethynylenesilylene)s were prepared. The heavy-metal effect in triplet-light-energy harvesting and the influence of the group 14 inorganic bridge on the phosphorescent properties of these organometallic materials were systematically examined. The photophysics and electronic structures of these silicon-linked organometallic compounds were studied as a function of the nature of E and oligomer chain length m.

    12. Synthesis and characterization of alt-copoly [oligosiloxane/1,4-bis(ethylenediphenylsilyl)benzene]s (pages 4825–4831)

      Thomas M. Gädda and William P. Weber

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21564

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      1,4-Bis(vinyldiphenylsilyl)benzene has been prepared and copolymerized with four α,ω-dihydrido oligosiloxanes by Pt-catalyzed hydrosilylation. Monomer and polymer structures were determined by 1H, 13C, 19F, and 29Si-NMR as well as IR and UV spectrometry. The polymers displayed thermal transitions characteristic to thermoplastic elastomers.

    13. Living anionic polymerization of N-methoxymethyl-N-isopropylacrylamide: Synthesis of well-defined poly(N-isopropylacrylamide) having various stereoregularity (pages 4832–4845)

      Mana Ito and Takashi Ishizone

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21583

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      Anionic polymerization of N-methoxymethyl-N-isopropylacrylamide and the following acidic deprotection gave poly(N-isopropylacrylamide)s [poly(NIPAM)] having predicted molecular weights and narrow molecular weight distributions (Mw/Mn = 1.1). Poly(NIPAM) obtained with Li+/Et2Zn initiator system possessed syndiotactic-rich configurations (r = 75–83%), while either atactic (r = 50%) or isotactic PNIPAM (r = 15–22%) was formed with K+/Et2Zn or Li+/LiCl initiator, respectively. Atactic and syndiotactic poly(NIPAM)s (42 < r < 83%) were water-soluble, whereas isotactic-rich one (r <31%) was insoluble in water. The cloud points of the aqueous solution of poly(NIPAM)s increased from 32 to 37 °C with the r-contents.

    14. Curing reaction of glycidylthioether resins: Kinetic model study by near infrared spectroscopy and multivariate curve resolution (pages 4846–4856)

      M. Garrido, M. S. Larrechi, F. X. Rius, J. C. Ronda and V. Cádiz

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21585

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      The reactivity of sulfur-based epoxy monomers was studied by monitoring of a model system involving phenylglycidylthioether and aniline. The reaction was carried out under isothermal conditions and monitored in situ by near infrared spectroscopy. Using multivariate curve resolution-alternating least squares made it possible to obtain the concentration and spectral profiles of each species throughout the reaction. To obtain the kinetic rate constants, the values of the recovered concentration profiles were fitted to a kinetic model proposed for the reaction.

    15. First synthesis of the bismole-containing conjugated polymer (pages 4857–4863)

      Yasuhiro Morisaki, Keita Ohashi, Hai-Sub Na and Yoshiki Chujo

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21590

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      We successfully synthesized the first conjugated polymer containing a bismuth atom in the conjugated main chain by incorporating a bismuth atom into the cyclopentadiene framework (bismole), which was constructed by the polymer reaction. A synthetic procedure and characterization of the obtained polymers were discussed in detail. This bismole-containing conjugated polymer exhibited moderate bluish green photoluminescence in solution.

    16. End-functionalization of polystyrene by malto-oligosaccharide generating aggregation-tunable polymeric reverse micelle (pages 4864–4879)

      Atsushi Narumi, Yutaka Miura, Issei Otsuka, Shin Yamane, Yoshikazu Kitajyo, Toshifumi Satoh, Akira Hirao, Noriaki Kaneko, Harumi Kaga and Toyoji Kakuchi

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21582

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      End-functionalized polystyrenes with saccharides, such as glucose, maltose, maltotriose, maltotetraose, maltopentaose, and maltohexaose, with a controlled molecular weight, narrow polydispersity, and quantitative end-functionality are described. The end-functionalized polymers were shown to generate polymeric reverse micelles in the good solvents for polystyrene, in which the molar masses and aggregation numbers were strongly related to the number of the glucose residues (n's) and the polymerization degrees of styrene (x).

    17. Library synthesis and characterization of 3-aminopropyl-terminated poly(dimethylsiloxane)s and poly(ϵ-caprolactone)-b-poly(dimethylsiloxane)s (pages 4880–4894)

      Abdullah Ekin and Dean C. Webster

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21593

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      To explore the effect of the polymer composition on the performance of these polymers in a coating system, libraries of 3-aminopropyl-terminated poly(dimethylsiloxane) and poly(ϵ-caprolactone)–poly(dimethylsiloxane)–poly(ϵ-caprolactone) triblock copolymers were synthesized. The synthesis was carried out in parallel with an automated high-throughput polymer synthesis system. The polymer libraries showed a systematic increase in the molecular weight of the poly(dimethylsiloxane) block and also of the poly(ϵ-caprolactone) block, as shown by the gel permeation chromatography molecular weight data.

    18. Glycopolymeric inhibitors of β-glucuronidase. III. Configurational effects of hydroxy groups in pendant glyco-units in polymers upon inhibition of β-glucuronidase (pages 4895–4903)

      Kazuhiko Hashimoto, Hiroshi Saito and Ryo Ohsawa

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21584

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      Two kinds of new glycopolymers, (P(VB-1-GlcaH-co-AAm), 9) and (P(VB-1-Glco-co-AAm), 10), were synthesized through the radical copolymerization of styrene derivatives bearing pendant D-glucaric and D-gluconic moieties, N-(p-vinylbenzyl)-1-D-glucaramide (VB-1-GlcaH, 7), and N-(p-vinylbenzyl)-D-gluconamide (VB-1-Glco, 8), with acrylamide (AAm). The glycopolymer 9 inhibited the hydrolysis of a model compound for xenobiotics-β-glucuronide conjugates, p-nitrophenyl β-D-glucuronide, uncompetitively, in contrast to the competitive inhibition in the presence of the corresponding isomeric glycopolymer (P(VB-6-GlcaH-co-AAm), 3) reported in our previous articles. On the other hand, copolymer 10 was found not to inhibit the hydrolysis. Not only existence of carboxy groups but also the configurational position of hydroxy groups in pendant glyco-units in macromolecular inhibitors may be essential for the interaction with β-glucuronidase.

    19. Electrosyntheses of high-quality freestanding poly(fluorene-co-3-methylthiophene) films with tunable fluorescence properties (pages 4904–4915)

      Zhenhong Wei, Jingkun Xu, Shouzhi Pu and Yukou Du

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21572

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      Poly(fluorene-co-3-methylthiophene), which had the advantages of both poly(3-methylthiophene) and polyfluorene, was electrosynthesized by the direct anodic oxidation of the monomer mixtures with a fluorene/3-methylthiophene feed ratio of 2:1 at a constant potential of 1.3 V (vs a saturated calomel electrode) in boron trifluoride diethyl etherate. Fluorescence spectroscopy studies revealed that the dedoped copolymer film in the solid state was a good blue-light emitter with a strong emission at 435 nm and a shoulder at 459 nm. The emitting properties of the copolymer could be tuned by parameters during the electrochemical copolymerization, such as the applied potential and monomer feed ratio.

    20. Effect of side-chain end groups on the optical, electrochemical, and photovoltaic properties of side-chain conjugated polythiophenes (pages 4916–4922)

      Erjun Zhou, Chang He, Zhan'Ao Tan, Chunhe Yang and Yongfang Li

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21581

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      Four side-chain conjugated polythiophene derivatives were synthesized by Wittig-Hornor reaction and GRIM method for investigating the effect of the conjugated side-chain structure on the properties of the polymers. The experiment results proved that electron-donor substitutent in the side-chains can make the absorption red-shift and reduce the bandgap effectively. The energy conversion efficiencies of photovoltaic cell based on P3DMOPVT reached 1.63%, increased by 140% in comparison with that of the device based on P3OPVT.

    21. Synthesis and characterization of new blue-light-emitting polymers based on PPP and PPV having fluorene pendant at vinyl bridge (pages 4923–4931)

      Yun-Hi Kim, Sang-Yun Jung, Sung Ouk Jung, Moon-Hak Park and Soon-Ki Kwon

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21579

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      The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m-phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m-phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed and synthesized by the Suzuki coupling and nickel(0)-mediated polycoupling.

  2. Notes

    1. Top of page
    2. Articles
    3. Notes
    1. You have free access to this content
      Five-coordinated active species in the stereoselective polymerization of rac-lactide using N,N′-(2,2-dimethyl-1,3-propylene) bis(3,5-di-tert-butyl-salicylideneimine) aluminum complexes (pages 4932–4938)

      Zhaohui Tang, Xuan Pang, Jingru Sun, Hongzhi Du, Xuesi Chen, Xianhong Wang and Xiabin Jing

      Article first published online: 17 JUL 2006 | DOI: 10.1002/pola.21578

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      The structure of active species generated from Al-achiral Salen complexes was discussed. The model complex (LAlOCH (CH3)COOCH3) of active species and living oligomer were synthesized and characterized. The single crystal X-ray diffraction and 1H, 13C, 27Al NMR were used to investigate the structure of the active species in the solid or solution state.

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