Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 3

1 February 2010

Volume 48, Issue 3

Pages 493–742

  1. Highlight

    1. Top of page
    2. Highlight
    3. Articles
    4. Notes
    5. Erratum
    1. You have free access to this content
      From polymeric particles to multifunctional nanocapsules for biomedical applications using the miniemulsion process (pages 493–515)

      Katharina Landfester, Anna Musyanovych and Volker Mailänder

      Article first published online: 18 DEC 2009 | DOI: 10.1002/pola.23786

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      Complex nanoparticles or nanocapsules can be obtained by the miniemulsion process. As polymers, inert or biodegradable polymers can be polymerized by different kinds of polymerization ranging from radical, anionic, cationic, or enzymatic polymerization to polycondensation or polyaddition. A functionalization of the surfaces can be obtained by using functional monomers that also allows further binding of cell receptors for specific cell targeting. Encapsulated materials such as fluorescent dyes or magnetic components can act as markers, hydrophobic, or hydrophilic drugs can be incorporated in the nanocapsules and can be released in a defined way by building release receptors in the shell.

  2. Articles

    1. Top of page
    2. Highlight
    3. Articles
    4. Notes
    5. Erratum
    1. Synthesis of thermal-stable and photo-crosslinkable polyfluorenes for the applications of polymer light-emitting diodes (pages 516–524)

      Pei-Hsuan Wang, Ming-Shou Ho, Sheng-Hsiung Yang, Kuei-Bai Chen and Chain-Shu Hsu

      Article first published online: 18 DEC 2009 | DOI: 10.1002/pola.23712

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      Three polyfluorenes, PFB, PFG and PFR were synthesized to fabricate red, green and blue and white PLED devices through photo-lithographic processes.

    2. Synthesis of refractive star-shaped polysulfide by anionic polymerization of phenoxy propylene sulfide using an initiating system consisting of trifunctional thiol derived from five-membered cyclic dithiocarbonate and amine (pages 525–531)

      Mitsuhiro Hirata, Bungo Ochiai and Takeshi Endo

      Article first published online: 18 DEC 2009 | DOI: 10.1002/pola.23742

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      Star-shaped poly(phenoxy propylene sulfide) [poly(PPS)] were synthesized by anionic polymerization using a trifuncitional initiator (I1) derived from a trifunctional five-membered cyclic dithiocarbonate and benzyl amine. Conditions for the anionic polymerization of PPS were optimized to obtain polymers with desired Mns and narrow Mw/Mns. The best catalyst and solvent were DBU and DMF, respectively. The star-shaped structure of the resulting star poly(PPS) were supported by SEC analysis. The refractive indexes (nD) of the star poly(PPS) were relatively high (>1.64).

    3. Preparation of molecularly imprinted polymers via atom transfer radical “bulk” polymerization (pages 532–541)

      Baiyi Zu, Ying Zhang, Xianzhi Guo and Huiqi Zhang

      Article first published online: 18 DEC 2009 | DOI: 10.1002/pola.23750

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      The first successful application of atom transfer radical “bulk” polymerization (ATRBP) in the molecular imprinting field is described, which afforded MIPs with obvious molecular imprinting effects towards the template, very fast template rebinding kinetics, and appreciable selectivity over structurally related compounds. In comparison with the MIP prepared via the traditional “bulk” free radical polymerization (BFRP), the MIPs prepared via ATRBP exhibited no improved binding properties, which is in contrast with the previously reported controlled molecular imprinting processes. This is tentatively ascribed to the occurrence of rather fast gelation process in ATRBP and the resultant uncontrolled polymerization.

    4. Synthesis of magnetic, reactive, and thermoresponsive Fe3O4 nanoparticles via surface-initiated RAFT copolymerization of N-isopropylacrylamide and acrolein (pages 542–550)

      Zhong-Peng Xiao, Kun-Min Yang, Hui Liang and Jiang Lu

      Article first published online: 18 DEC 2009 | DOI: 10.1002/pola.23752

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      A RAFT agent was anchored onto Fe3O4 nanoparticles in a simple procedure using a ligand exchange reaction of S-1-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)trithiocarbonate (DDMAT) with oleic acid initially present on the surface of oleic acid-stabilized Fe3O4 nanoparticles. DDMAT-functionalized Fe3O4 nanoparticles were then used for the surface-initiated RAFT copolymerization of N-isopropylacrylamide (NIPAM) and acrolein to fabricate structurally well-defined hybrid nanoparticles with reactive and thermoresponsive poly(NIPAM-co-acrolein) shell and magnetic Fe3O4 core. This novel magnetic nanoparticle exhibited temperature-trigged magnetic separation behavior and high ability to immobilize protein.

    5. Photoresponsive nanocarriers based on PAMAM dendrimers with a o-nitrobenzyl shell (pages 551–557)

      Yan Li, Xinru Jia, Min Gao, Hai He, Guichao Kuang and Yen Wei

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23757

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      A series of PAMAM dendrimers with o-nitrobenzyl groups at the periphery were synthesized. Their photolysis, guest encapsulation, and releasing behaviors were studied.

    6. A green epoxidation system with poly(4-vinylpyridine) microsphere-supported molybdenum catalyst (pages 558–562)

      Lijing Cao, Mu Yang, Ge Wang, Yen Wei and Dongbai Sun

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23760

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      A “green” epoxidation system has been developed with relatively environment-benign hydrogen peroxide, ethanol, and poly(4-vinylpyridine) microsphere-supported molybdenum as oxidant, solvent, and catalyst, respectively. The system yielded nearly quantitative selectivity and conversion in the epoxidation of alkenes such as cis-cyclooctene with an excellent reusability.

    7. Preparation and characterization of a poly(vinylbenzyl sulfonic acid)-grafted FEP membrane (pages 563–569)

      Geng Fei, Junhwa Shin, Sung-A Kang, Beom-Seok Ko, Phil-Hyun Kang, Youn-Sik Lee and Young Chang Nho

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23762

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      A novel polymer electrolyte membrane, FEP-g-PVBSA, has been successfully prepared by using a simultaneous irradiation grafting of vinylbenzyl chloride monomer onto a poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) film and taking subsequent chemical modification steps to modify the benzyl chloride moiety to the benzyl sulfonic acid moiety.

    8. Kinetic study of the polymerization of aromatic polyurethane prepolymers by high-throughput experimentation (pages 570–580)

      László I. Majoros, Bernard Dekeyser, Richard Hoogenboom, Martin W. M. Fijten, Jan Geeraert, Nancy Haucourt and Ulrich S. Schubert

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23768

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      A high-throughput experimental setup has been developed and applied for the screening of aromatic-based polyurethane prepolymers. The polymerizations have been performed in solution by an automated parallel synthesizer, and the obtained kinetic parameters have been compared with the conventional, bulk polymerization results. In spite of the complexity of the curing process of these resins, the results obtained by high-throughput solution polymerizations can be applied for evaluating the bulk polymerization processes.

    9. Synthesis and characterization of physical crosslinking systems based on cyclodextrin inclusion/host-guest complexation (pages 581–592)

      Ethem Kaya and Lon J. Mathias

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23771

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      New supramolecular assemblies based on cyclodextrin and adamantane were prepared. Two methacrylate monomers bearing cyclodextrin and adamantane were synthesized, and copolymerized with poly(ethylene glycol) methyl ether methacrylate by free radical polymerization. All copolymers showed two distinct glass transitions. The specific interaction between pendent adamantyl and cyclodextrin was examined by 1H-NMR. The viscoelastic properties of supramolecular assemblies were investigated with frequency and temperature sweep experiments. The specific host-guest interaction between pendent adamantyl and cyclodextrin lead to large increases of the viscosity; and depending on the concentration of these groups, also to gel formation.

    10. Synthesis of oily core-hybrid shell nanocapsules through interfacial free radical copolymerization in miniemulsion: Droplet formation and nucleation (pages 593–603)

      Z. H. Cao, G. R. Shan, N. Sheibat-Othman, J.-L. Putaux and E. Bourgeat-Lami

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23809

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      Nanocapsules with an oily core and a hybrid Styrene-MPS-NIPAM copolymer shell were elaborated through polymerization-induced phase separation in miniemulsion. The effect of the nature of the oil phase, the monomer content and the surfactant concentration on the size and size distribution of the miniemulsion droplets was investigated in details. The nanocapsules were characterized by TEM and cryo-TEM. Both nanocapsules and nanoparticles were produced by polymerization of the miniemulsion. The proportion of nanoparticles increased with increasing monomer concentration in the oil phase and decreased with the addition of NIPAM.

    11. Kinetic model of reversible addition-fragmentation chain transfer polymerization in microemulsions (pages 604–613)

      Jennifer M. O'Donnell and Eric W. Kaler

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23811

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      A simple kinetic model of RAFT microemulsion polymerization has been developed. This model captures both the decrease in the rate of polymerization, and the shift of the rate maximum to conversions less than the 39% conversion predicted by the Morgan model for uncontrolled microemulsion polymerizations as the chain transfer agent per micelle ratio increases. The model shows that slow fragmentation of the macroRAFT radical induces an increase in termination reactions, and thus causes the observed rate retardation in RAFT microemulsion polymerizations of butyl acrylate with methyl-2-(O-ethylxanthyl)propionate.

    12. Poly(3-hexylthiophene)-b-poly(3-cyclohexylthiophene): Synthesis, microphase separation, thin film transistors, and photovoltaic applications (pages 614–626)

      Pei-Tzu Wu, Guoqiang Ren, Felix S. Kim, Chaoxu Li, Raffaele Mezzenga and Samson A. Jenekhe

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23812

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      New diblock conjugated copolymers, poly(3-hexylthiophene)-b-poly(3-cyclohexylthiophene), undergo microphase-separation into crystalline domains with sizes of 17–22nm. Two distinct interlayer stacking distances (1.69 and 1.40 nm) due to the different side chains were found in the crystalline lamellar structure. Field-effect transistors with high mobility (0.0019 cm2/Vs) and efficient (2.45%) bulk heterojunction solar cells were demonstrated using the new block copolymers.

    13. Thermoresponsive fluorescent water-soluble copolymers containing BODIPY dye: Inhibition of H-aggregation of the BODIPY units in their copolymers by LCST (pages 627–634)

      Atsushi Nagai, Kenta Kokado, Junpei Miyake and Yoshiki Cyujo

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23813

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      Novel water-soluble copolymers, composed of (2-dimethylamino)ethyl methacrylate (DMAEMA) and 4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes, were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization. The copolymers led to thermoresponsive polymers having phase separation temperatures at 32–40 °C, respectively, depending on the compositions of hydrophilic/hydrophobic balances. Further, the effective reversible decrease/increase of the emission intensity of the copolymers led to the reversible formation/inhibition of the H-aggregation between two BODIPY planes in the copolymers on heating and cooling across the border of LCST.

    14. Synthesis and properties of phenothiazylene vinylene-based polymers: New organic semiconductors for field-effect transistors and solar cells (pages 635–646)

      Seon-Kyoung Son, Yoon-Suk Choi, Woo-Hyung Lee, Yongtaek Hong, Jae-Ryoung Kim, Won-Suk Shin, Sang-Jin Moon, Do-Hoon Hwang and In-Nam Kang

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23814

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      A series of new phenothiazylene vinylene-based semiconducting polymers (P1, P2, and P3) have been synthesized via a Horner-Emmons reaction with weight-averaged molecular weight (Mw) around 22,000–29,000. Solution–processed field-effect transistors fabricated from these polymers showed p-type organic thin-film transistor characteristics. The field-effect mobilities of P1, P2, and P3 were measured to be 1.0 × 10−4, 3.6 × 10−5, and 1.0 × 10−3 cm2 V−1 s−1, respectively, and the on/off ratios were on the order of 102 for P1 and P2, and 103 for P3. The atomic force microscopy images of the polymer thin films revealed that all polymers were characterized by an amorphous structure. A photovoltaic device in which a P3/PC71BM (1/5) blend film was used as the active layer exhibited an open-circuit voltage (VOC) of 0.42 V, a short circuit current (JSC) of 5.17 mA cm−2, a fill factor of 0.35, and a power conversion efficiency of 0.76% under AM 1.5 G (100 mW cm−2) illumination.

    15. Thermoresponsive PPEGMEA-g-PPEGEEMA well-defined double hydrophilic graft copolymer synthesized by successive SET-LRP and ATRP (pages 647–655)

      Sujuan Zhai, Beidi Wang, Chun Feng, Yongjun Li, Dong Yang, Jianhua Hu, Guolin Lu and Xiaoyu Huang

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23815

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      A series of well-defined double hydrophilic graft copolymers, consisting of poly[poly(ethylene glycol) methyl ether acrylate] (PPEGMEA) backbone and poly[poly(ethylene glycol) ethyl ether methacrylate] (PPEGEEMA) side chains, were synthesized by sequential single electron transfer-living radical polymerization (SET-LRP) and atom transfer radical polymerization (ATRP). The molecular weights of both the backbone and the side chains were controllable and the molecular weight distributions kept narrow (Mw/Mn ≤ 1.20). This kind of double hydrophilic copolymer is stimuli-responsive to both temperature and ion.

    16. Synthesis of highly refractive and transparent polyimides derived from 4,4′-thiobis[2″,6″-dimethyl-4″-(p-phenylenesulfanyl)aniline] (pages 656–662)

      Nam-Ho You, Tomoya Higashihara, Shinji Ando and Mitsuru Ueda

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23817

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      New aromatic diamines with methyl groups at the ortho position have been developed to prepare highly transparent aromatic polyimides (PIs) in the visible region. All PIs show good thermal stability and optical properties, such as optical transparency higher than 75% at 450 nm for a thickness of about 10 μm, glass transition temperatures in the range of 196.7–217.8 °C, and thermal decomposition temperatures (T10%) in the range of 497.2–500.2 °C while maintaining relatively high refractive indices ranging from 1.7135 to 1.7301.

    17. Oxygen-sensing properties of 5,10,15,20-tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate) (pages 663–670)

      Makoto Obata, Noriko Matsuura, Kazunori Mitsuo, Hiroki Nagai, Keisuke Asai, Masafumi Harada, Shiho Hirohara, Masao Tanihara and Shigenobu Yano

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23818

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      To reduce microheterogeneity of the sensing film of pressure-sensitive paint (PSP), poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate)s bearing 5,10,15,20-tetraphenylporphyrinato palladium(II) (PdTPP) and platinum(II) (PtTPP) were synthesized and the optical properties of films of these dye-pendant polymers and conventional mixtures of polymer and dye (dye-mixed polymers) were compared by means of steady-state luminescence quenching and transient luminescence decay measurements. A two-site model fitted the experimental data, suggesting the existence of two distinct microheterogeneities, one temperature-dependent and the other temperature-independent. The dye-conjugation approach efficiently reduces the former microheterogeneity, but not the latter.

    18. Macrocyclization of polymers via ring-closing metathesis and azide/alkyne-“click”-reactions: An approach to cyclic polyisobutylenes (pages 671–680)

      Matthias Schulz, Susanne Tanner, Haitham Barqawi and Wolfgang H. Binder

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23820

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      The end-to-end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring-closing metathesis (RCM) or the azide/alkyne-“click”-reaction combined with a subsequent “click”-reaction to remove linear species. Azide/alkyne-“click”-reactions of bisalkyne-telechelic PIB's (Mn = 3840 and 9820 gmol−1) with excess of 1,11-diazido-undecane lead to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide-moieties in the linear PIB's with excess of alkyne-telechelic PEO enabled the chromatographic removal of the resulting linear PEO-PIB-block copolymers by column chromatography leading to cyclic PIB's devoid of linear contaminants.

    19. Unimolecular micelle derived from hyperbranched polyethylenimine with well-defined hybrid shell of poly(ethylene oxide) and polystyrene: A versatile nanocapsule (pages 681–691)

      Yong Liang, Decheng Wan, Xiangyu Cai, Ming Jin and Hongting Pu

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23821

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      A macromolecular nanocapsule with a hybrid shell of PEO and PS can switch to three-layer onion-like particle, the particle can exist in the form of unimolecular micelle and simultaneously encapsulate both ionic and apolar guests.

    20. Polyethylene/graphite nanocomposites obtained by in situ polymerization (pages 692–698)

      Fabiana de C. Fim, Jonathan M. Guterres, Nara R. S. Basso and Griselda B. Galland

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23822

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      Polyethylene/graphite nanocomposites, with graphite amounts of 1.2, 2.8 and 5.6 wt %, were obtained by in situ polymerization, with good catalytic activity. XRD and TEM analysis showed that graphite nanosheets of large aspect ratio were well dispersed throughout the polymeric matrix.

    21. The relationship between catalyst precursors and chain end groups in homogeneous propene polymerization catalysis (pages 699–708)

      Lucia Caporaso, Claudio De Rosa and Giovanni Talarico

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23831

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      Why metallocene systems promote the selective formation of cis but-2-enyls end group after a 2,1 inserted unit, whereas for postmetallocene catalysts, chain release promotes exclusively the formation of allyl terminated chain end?

    22. Synthesis and thermoreversible gelation of dendron-like polypeptide/linear poly(ε-caprolactone)/dendron-like polypeptide triblock copolymers (pages 709–718)

      Yuan You, Yi Chen, Chong Hua and Chang-Ming Dong

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23834

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      Dendron-like poly(γ-benzyl-L-glutamate)/linear poly(ε-caprolactone)/dendron-like poly(γ-benzyl-L-glutamate) triblock copolymers having 2m+1 PBLG branches were successfully synthesized by utilizing ring-opening polymerization and click chemistry. The crystallinity of the central PCL segment is increasingly suppressed by the flanking PBLG wedges, whereas the PBLG branches within these copolymers gradually changed from a β-sheet conformation to an α-helix conformation. These triblock copolymers formed thermoreversible organogels in toluene, and the critical gelation concentration decreased gradually with the increasing PBLG branches. The gelation occurred through a self-assembled nanoribbon mechanism.

    23. Specific lectin interactions and temperature-induced reversible gels in novel water-soluble glycopolymers bearing maltotrionolactone pendant groups (pages 719–729)

      M. L. Cerrada, M. Sánchez-chaves, C. Ruiz and M. Fernández-García

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23837

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      Glycopolymers containing diaminobutylmaltotrionolactone pendant groups with different composition and linkage between the backbone and carbohydrate pendant groups present an interesting water-solution behavior. The reversible gels from the glycopolymers activated with p-nitrophenyl carbonate groups are developed at lower temperatures than those incorporating o-phthalic acid ones. In addition, all of these glycopolymers exhibit specific lectin interaction with Concanavalin A.

  3. Notes

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    3. Articles
    4. Notes
    5. Erratum
    1. Self-assembled dendron nanotubes: Surface functionalization with maltosyl units and their reversible complexation with Concanavalin A (pages 730–734)

      Mikyoung Yun, Chiyoung Park, Jeonghun Lee and Chulhee Kim

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23801

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      We described a facile methodology to construct the dendron nanotubes with surface maltosyl unit which can interact specifically with a protein such as Con A. The inclusion of the focal pyrene moiety of the amide dendron into the cavity of 6-O-monomaltosyl-β-CD induced formation of the self-assembled dendron nanotubes which contain maltosyl-CD units on the surface. We investigated not only the complexation of the dendron nanotube with Con A but also dissociation of the complex by using glucose which binds to Con A more strongly than maltose.

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      ATRP of 2-vinylpyridine and tert-butyl acrylate mixtures giving precursors of polyampholytes (pages 735–741)

      Eva Čadová, Jiří Konečný, Jaroslav Kříž, Romana Svitáková, Petr Holler, Jan Genzer and Petr Vlček

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23805

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      Statistical copolymers of 2-vinylpyridine and tert-butyl acrylate were first synthesized by ATRP using methyl 2-bromopropanoate/CuCl/Me4Cyclam system and transformed to ampholytic poly(2-vinylpyridine-co-acrylic acid). Monomer reactivity ratios of 2-VPy and t-BuA were determined by extended Kelen-Tüdos method and by COPOINT program on the basis of NMR spectra and elemental analysis of the prepared copolymers.

  4. Erratum

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    2. Highlight
    3. Articles
    4. Notes
    5. Erratum
    1. You have free access to this content
      Supramacromolecular chemistry: Self-assembly of polystyrene-based multi-armed pseudorotaxane star polymers from multi-topic C60 derivatives (page 742)

      Harry W. Gibson, Zhongxin Ge, Jason W. Jones, Kim Harich, Adam Pederson and Harry C. Dorn

      Article first published online: 22 DEC 2009 | DOI: 10.1002/pola.23856

      This article corrects: