Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 15

1 August 2012

Volume 50, Issue 15

Pages i–iv, 2981–3224

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      Cover Image, Volume 50, Issue 15 (pages i–ii)

      Article first published online: 22 JUN 2012 | DOI: 10.1002/pola.26213

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      Graphene nanosheets possess extraordinary physical and electrical properties with enormous potential for applications in microelectronics, photonic devices and nanocomposite materials. However, single graphene platelets tend to undergo agglomeration, which significantly compromises the final material properties. One of the strategies to overcome this problem is to modify graphene (or graphene oxide) with polymer brushes. The present Highlight article from Albert Badri, Michael R. Whittaker, and Per B. Zetterlund on page 2981 describes research efforts to date in this area, focusing on the use of controlled/living radical polymerization techniques.

    2. You have free access to this content
      Inside Cover, Volume 50, Issue 15 (pages iii–iv)

      Article first published online: 22 JUN 2012 | DOI: 10.1002/pola.26214

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      Rare earth tris(borohydride) complexes, Ln(BH4)3(THF)3 (Ln = Sc, Y, La and Dy), are highly efficient single-component catalysts for ring opening polymerizations of α-amino acid N-carboxyanhydrides (NCAs) as presented by H. Peng, J. Ling, Y. Zhu, L. You, and Z. Shen on page 3016. Homopolypeptides and block copolypeptides with relatively narrow molecular weight distributions (as low as 1.14) can be prepared. Polymerization mechanism studies show that at room temperature, two reaction pathways occur simultaneously producing α-hydroxyl-ω-aminotelechelic and α-carboxylic-ω-aminotelechelic polypeptides. However, when the temperature is decreased to 0°C, one of the reaction pathways can be efficiently depressed affording α-hydroxyl-ω-aminotelechelic polypeptide exclusively.

  2. Highlight

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      Modification of graphene/graphene oxide with polymer brushes using controlled/living radical polymerization (pages 2981–2992)

      Albert Badri, Michael R. Whittaker and Per B. Zetterlund

      Article first published online: 8 MAY 2012 | DOI: 10.1002/pola.26094

      Thumbnail image of graphical abstract

      Graphene nanosheets possess extraordinary physical and electrical properties with enormous potential for applications in microelectronics, photonic devices and nanocomposite materials. However, single graphene platelets tend to undergo agglomeration, which significantly compromises the final material properties. One of the strategies to overcome this problem is to modify graphene (or graphene oxide) with polymer brushes. This article describes research efforts to date in this area, focusing on the use of controlled/living radical polymerization techniques.

  3. Rapid Communication

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      Lewis acid-specific polymerization behaviors in living cationic polymerization of vinyl ether with a malonate group (pages 2993–2998)

      Yukari Oda, Tomohiro Tsujino, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26088

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      For the precision synthesis of carboxy-functional polymers, the cationic polymerization of a malonic ester-containing vinyl ether (VOEM) was examined with various Lewis acids in the presence of an added base. Living cationic polymerization was achieved using ZnCl2, FeCl3, and SnCl4 in conjunction with a suitable added base, whereas TiCl4 and Et1.5AlCl1.5 only led to oligomerization. Such significant differences in polymerization behavior resulted from the interactions of the diester groups with a particular Lewis acid.

  4. Original Articles

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. High density cationic polymer brushes from combined “click chemistry” and RAFT-mediated polymerization (pages 2999–3007)

      Serkan Demirci and Tuncer Caykara

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26087

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      Cationic poly[(ar-vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes on a silicon surface were prepared by the combined technology of “click chemistry” and reversible addition-fragmentation chain transfer polymerization. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(VBTAC) brushes (0.78 chains/nm2).

    2. Irreversible helix rearrangement from Cis-transoid to Cis-cisoid in poly(p-n-hexyloxyphenylacetylene) induced by heat-treatment in solid phase (pages 3008–3015)

      Asahi Motoshige, Yasuteru Mawatari, Yoshiaki Yoshida, Chigusa Seki, Haruo Matsuyama and Masayoshi Tabata

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26089

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      Poly(p-n-hexyloxyphenylacetylene)s (PpHPA), prepared by using [Rh(norbornadine)Cl]2-NEt3 catalyst and ethanol and n-hexane as polymerization solvents at 25 °C afforded a yellow PpHPA, poly(Y), and a red polymer, poly(R), respectively, in high yields and high helical cis-transoid ratios. Their color differences were explained by formation of stretched cis-transoid and stable contracted cis-cisoid helices, respectively. Poly(Y) was irreversibly transformed to a reddish-black polymer, poly(Y[RIGHTWARDS ARROW]B), whose spectral data were similar to those of poly(R) when poly(Y) was heated at 80 °C in N2 gas for 1 h.

    3. Polymerization of α-amino acid N-carboxyanhydrides catalyzed by rare earth tris(borohydride) complexes: Mechanism and hydroxy-endcapped polypeptides (pages 3016–3029)

      Hui Peng, Jun Ling, Yinghong Zhu, Lixin You and Zhiquan Shen

      Article first published online: 21 APR 2012 | DOI: 10.1002/pola.26077

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      Rare earth tris(borohydride) complexes, Ln(BH4)3(THF)3 (Ln = Sc, Y, La, and Dy), are efficient catalysts to prepare homopolypeptides and block copolypeptides with relatively narrow molecular weight distributions in the range of 1.1 to 1.6. Polymerization mechanism studies indicate that both 5-CO and 3-NH are involved in the initiation process resulting in α-hydroxyl-ω-aminotelechelic and α-carboxylic-ω-aminotelechelic polypeptides. By decreasing the reaction temperature, the unprecedented α-hydroxyl-ω-aminotelechelic polypeptide can be selectively synthesized.

    4. Bisphosphonate units in the main polymer chain: The first synthesis (pages 3030–3038)

      Stanislaw Penczek, Krzysztof Kaluzynski and Julia Pretula

      Article first published online: 14 MAY 2012 | DOI: 10.1002/pola.26083

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      Synthesis of polymers with bisphosphonic acid units in the main chain has been described for the first time. In the radical copolymerization of tetraethyl vinylidene phosphonate (B) with vinyl acetate alternating copolymer was obtained whereas in copolymerization of (B) with acrylic acid macromolecules with blocks of acrylic acid separated with single bisphosphonate units were formed.

    5. Main-chain functionalization of poly(L-lactide) with pendant unsaturations (pages 3039–3045)

      Peter Olsén, Karin Odelius and Ann-Christine Albertsson

      Article first published online: 25 APR 2012 | DOI: 10.1002/pola.26084

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      Main-chain functionalized poly(L-lactide) (PLLA) with pendant unsaturations was synthesized through a one-pot postpolymerization procedure with the PLLA homopolymer as the starting material. The material was functionalized through α-hydrogen abstraction by a sterically hindered strong base, lithium diisopropylamide, followed by the addition of an acid chloride. This yielded a material with a high molar ratio of incorporated unsaturated fatty acid structures to PLLA repeating units together with some reduction of the initial molecular weight. The unsaturations were preserved under the reaction and the material exhibited surfactant-like properties in blends with oleic acid and PLLA.

    6. Synthesis and radical polymerization of styrene-based monomer having a five-membered cyclic carbonate structure (pages 3046–3051)

      Takahiro Miyata, Kozo Matsumoto, Takeshi Endo, Shigeaki Yonemori and Shoji Watanabe

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26090

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      A styrene-based monomer having a five-membered cyclic carbonate structure (4-vinylbenzyl 2,5-dioxoran-3-ylmethyl ether, VBCE) was prepared by addition of carbon dioxide to 4-vinylbenxyl glycidyl ether. Polymerization of the VBCE readily proceeded using 2,2′-azobisisobutyronitrile as an initiator to give polyVBCE.

    7. Synthesis of gradient copolymers with simultaneously tailor-made chain composition distribution and glass transition temperature by semibatch ATRP: From modeling to application (pages 3052–3066)

      Yin-Ning Zhou, Jin-Jin Li and Zheng-Hong Luo

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26091

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      A systematic study was carried out on the preparation of poly(MMA-grad-HEMA) gradient copolymers as a potential excellent damping material with a simultaneously tailor-made chain composition distribution and Tg through semibatch ATRP. The model prediction for the instantaneous composition, molecular weight, polydispersity index, monomer conversion, polymer mass, and Tg breadths exhibited by normal and inverse gradient copolymer versus the polymerization time was in accordance with the experimental results.

    8. Effect of catalyst systems and reaction conditions on the synthesis of cellulose-g-PDMAam copolymers by controlled radical polymerization (pages 3067–3076)

      Miia Hiltunen, Joonas Siirilä and Sirkka Liisa Maunu

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26092

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      Water-soluble cellulose-g-poly(N,N-dimethylacrylamide) copolymer is synthesized via controlled radical polymerization using softwood pulp-based cellulose macroinitiator in homogeneous phase. Besides the synthetic aspect, the effects of the DP of the PDMAam grafts and the grafting density on the aqueous solution properties of the cellulose-g-PDMAam copolymers are studied in more detail by means of steady-shear viscosity and dynamic light scattering measurements.

    9. Effect of reaction conditions on film morphology of polyaniline composite membranes for gas separation (pages 3077–3085)

      Natalia V. Blinova, Jaroslav Stejskal, Jean M. J. Fréchet and Frantisek Svec

      Article first published online: 21 APR 2012 | DOI: 10.1002/pola.26093

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      Novel composite membranes combining a 90–200 nm thick active layer of polyaniline attached to a polypropylene support have been prepared using in situ precipitation, dispersion, or emulsion polymerization of aniline with simultaneous deposition on top of the porous support. The effect of reaction conditions on both the formation and the quality of the polyaniline layers was demonstrated. Selective separation of carbon dioxide from its mixture with methane illustrates potential application of these membranes.

    10. Synthesis, reactivity, and optoelectronic properties of poly(3-alkenylthiophene) diblock copolymers (pages 3086–3094)

      Mahesh P. Bhatt, Martin K. Huynh, Prakash Sista, Hien Q. Nguyen and Mihaela C. Stefan

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26095

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      The synthesis of poly(3-hexylthiophene)-b-poly(3-pentenylthiophene) and poly(3-hexyl- thiophene)-b-poly(3-undecenylthiophene) diblock copolymers is reported. Post-polymerization chemical modification of diblock copolymers demonstrated the reactivity of the alkenyl substituents. Poly(3-hexylthiophene)-b-poly(3-pentenylthiophene-g-polyethylene) graft copolymer was synthesized by ring-opening metathesis polymerization using the poly(3-hexylthiophene)-b-poly(3-pentenylthiophene) as a transfer agent. The synthesized polymers have good optoelectronic properties and morphologies similar to regioregular poly(3-hexylthiophene).

    11. Synthesis of branch-ring-branch tadpole-shaped [linear-poly(ε-caprolactone)]-b-[cyclic-poly(ethylene oxide)]-b- [linear-poly(ε-caprolactone)] by combination of glaser coupling reaction with ring-opening polymerization (pages 3095–3103)

      Xiaoshan Fan, Tingting Tang, Kun Huang, Guowei Wang and Junlian Huang

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26096

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      A novel amphiphilic branch-ring-branch tadpole-shaped [linear-poly(ε-caprolactone)]-b-[cyclic-poly(ethylene oxide)]-b-[linear-poly(ε-caprolactone)] [(l-PCL)-b-(c-PEO)-b-(l-PCL) was synthesized by combination of glaser coupling reaction with ring-opening polymerization (ROP) mechanism. The π-shaped analogs of poly(ε-caprolactone)/poly(ethylene oxide)]-b-poly(ethylene oxide)-b-[poly(ε-caprolactone)/poly(ethylene oxide) [(PEO/PCL)-b-PEO-b-(PCL/PEO)] were similarly synthesized. The self-assembling behaviors of (l-PCL)-b-(c-PEO)-b-(l-PCL) and (PEO/PCL)-b-PEO-b-(PCL/PEO) with comparable molecular weight in water were preliminarily investigated and compared.

    12. Bioactive mesoglobules of poly(di(ethylene glycol) monomethyl ether methacrylate)–peptide conjugate (pages 3104–3115)

      Roza Trzcinska, Dawid Szweda, Stanislav Rangelov, Piotr Suder, Jerzy Silberring, Andrzej Dworak and Barbara Trzebicka

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26097

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      The synthesis and self-assembly of a well-defined thermosensitive conjugate: poly(di(ethylene glycol) monomethyl ether methacrylate)-block-GRKFG-Dns pentapeptide is described. The bioconjugate aggregated in dilute aqueous solution, above TCP, forming spherical particles (mesoglobules) surrounded by a peptide shell. The peptide moiety in the bioconjugate retained its biological activity and was available for enzymatic hydrolysis even when the macromolecules were aggregated to mesoglobules.

    13. Postfunctionalization of polyoxanorbornene via sequential Michael addition and radical thiol-ene click reactions (pages 3116–3125)

      Hakan Durmaz, Muge Butun, Gurkan Hizal and Umit Tunca

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26098

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      Poly(oxanorbornene imide) with two different orthogonal functionalities, main chain vinyl and side chain acrylate, is selectively functionalized via sequential two thiol-ene click reactions, nucleophilic thiol-ene coupling via Michael addition and photoinduced radical thiol-ene. The orthogonal reactivity of two diverse double bonds, vinyl and acrylate functionalities, for the abovementioned consecutive thiol-ene click reactions was first demonstrated on the model compound.

    14. Synthesis and characterization of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-grafted-poly(acrylonitrile) via single electron transfer–living radical polymerization process (pages 3126–3134)

      Xin Hu, Junjie Li, Huayi Li and Zhicheng Zhang

      Article first published online: 25 APR 2012 | DOI: 10.1002/pola.26099

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      Poly(vinylidene fluoride-co-chlorotrifluoroethylene)-grafted-polyacrylonitrile (P(VDF-co-CTFE)-g-PAN) has been successfully synthesized via single electron transfer–living radical polymerization (SET–LRP) initiated with P(VDF-co-CTFE) and catalyzed with trace amount of Cu(0)/tris(2(dimethylamino)ethyl)amine. The typical side reactions happening on P(VDF-co-CTFE) in atom transfer radical polymerization could be avoided in SET–LRP thanks to the mild reaction conditions. Well-controlled polymerization character has been observed under varied reaction conditions. The introduction of PAN side chain reduces both crystalline and thermal property of P(VDF-co-CTFE)s.

    15. Synthesis and properties of monocleavable amphiphilic comblike copolymers with alternating PEG and PCL grafts (pages 3135–3148)

      Shixian Li, Chunnuan Ye, Guangdong Zhao, Meijing Zhang and Youliang Zhao

      Article first published online: 25 APR 2012 | DOI: 10.1002/pola.26100

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      Well-defined disulfide-linked comblike copolymers with alternating PCL and PEG pendent chains were synthesized and applied for in vitro release of DOX. Comblike copolymers with similar compositions usually exhibited lower crystallization temperature, melting temperature, and crystallinity than their linear analogs, indicating the influence of macromolecular architecture on physicochemical properties. In contrast to linear copolymer aggregates with similar compositions, comblike copolymer aggregates with disulfide linkage had improved storage stability and enhanced DLE and could rapidly release the encapsulated drug when triggered by 10 mM DTT. These reduction-sensitive, biocompatible, and biodegradable aggregates have a potential as controlled delivery vehicles.

    16. Controllable glycosylation of polyphosphazene via radical thiol–yne click chemistry (pages 3149–3157)

      Ning Ren, Xiao-Jun Huang, Xu Huang, Yue-Cheng Qian, Cang Wang and Zhi-Kang Xu

      Article first published online: 25 APR 2012 | DOI: 10.1002/pola.26101

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      A versatile approach based on “thiol–yne” click chemistry has been developed for the synthesis of glycosylated polyphosphazenes with controllable density of glycosyl groups. The substitution of alkyne/alkane mixture was conducted to reduce the alkyne density in the side groups of polyphosphazenes and minimize the influences of this steric effect. The glycosylated polyphosphazene is able to form into polymer particles through self-assembly process.

    17. Formation of a crosslinked POSS network by an unusual hydrosilylation: Thermo-oxidative stabilization of the α-cristobalite phase in its amorphous regions (pages 3158–3170)

      Manoj K. Kolel-Veetil, Kenan P. Fears, Syed B. Qadri, Christopher A. Klug and Teddy M. Keller

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26102

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      A crosslinked network with POSS cores formed by an unusual hydrosilylation reaction was thermally treated in either argon or air up to 1000 °C. The symmetrically-functionalized POSSs, in fluorite silica phase, remained unchanged on thermal treatment due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α-cristobalite phase, which is typically formed upon cooling by a β- to α-transition of the β-cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air.

    18. Synthesis of periodic copolymers via ring-opening copolymerizations of cyclic anhydrides with tetrahydrofuran using nonafluorobutanesulfonimide as an organic catalyst and subsequent transformation to aliphatic polyesters (pages 3171–3183)

      Tang Tang, Miyuki Oshimura, Shinji Yamada, Akinori Takasu, Xiaoping Yang and Qing Cai

      Article first published online: 8 MAY 2012 | DOI: 10.1002/pola.26103

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      Ring-opening copolymerizations of cyclic anhydrides with THF catalyzed by Nf2NH are performed at high temperature (100–120 °C) to produce polyesters (Mn = 0.8–6.8 × 103, Mn/Mw = 2.03–3.51). Ether units were temporarily formed during the process and subsequently transformed into esters by chain transfer reaction. At low temperature (25–50 °C), poly(ester-ether) (Mn = 3.4–12.1 × 103, Mw/Mn = 1.44–2.10) is produced. When toluene is used as a solvent, periodic copolymers can be polymerized via reaction of GAn with THF (unit ratio: 1:2) (Mn = 5.9 × 103, Mw/Mn = 2.10).

    19. Molecular captain: A light-sensitive linker molecule in poly(ethylene glycol)-poly(L-alanine)-poly(ethylene glycol) triblock copolymer directs molecular nano-assembly, conformation, and sol-gel transition (pages 3184–3191)

      So Young Jeong, Hyo Jung Moon, Min Hee Park, Min Kyung Joo and Byeongmoon Jeong

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26104

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      A light-sensitive azobenzene group (Z) was incorporated in a temperature-sensitive poly(ethylene glycol)-poly(L-alanine) (PEG-PA) block copolymer to form PEG-PA-Z-PA-PEG. The azobenzene group underwent a trans–cis configuration change upon exposure to UV and vis light. The single azobenzene molecule embedded in the middle of a rigid core of the block copolymer significantly affected molecular self-assembly of the rigid (PA)-flexible (PEG) type block copolymer in water as well as sol-to-gel transition temperature of the polymer aqueous solution, depending on its exposure to UV or vis light.

    20. Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains (pages 3192–3205)

      Alexander M. Breul, Johann Schäfer, Georgy M. Pavlov, Anke Teichler, Stephanie Höppener, Christine Weber, Jürgen Nowotny, Lars Blankenburg, Jürgen Popp, Martin D. Hager, Benjamin Dietzek and Ulrich S. Schubert

      Article first published online: 17 MAY 2012 | DOI: 10.1002/pola.26105

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      A series of three polymerizable oligo phenylene ethynylenes on the basis of substituted methacrylates was synthesized and subsequently polymerized. The optical behavior of all three monomer units was tuned by the choice of the substituents on the conjugated side chains. The donor and acceptor group containing polymers showed resonant energy transfer from the donor to the acceptor groups.

    21. Phospha-Michael addition to enone-containing triglyceride derivatives as an efficient route to flame retardant renewable thermosets (pages 3206–3213)

      Maryluz Moreno, Gerard Lligadas, Joan C. Ronda, Marina Galià and Virginia Cádiz

      Article first published online: 6 MAY 2012 | DOI: 10.1002/pola.26106

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      Enone-containing high-oleic sunflower oil has been converted to a flame retardant thermoset through phospha- and aza-Michael additions. Microwave irradiation induced crosslinking was shown to be a valuable alternative to conventional heating for both processes. The obtained limiting oxygen index values demonstrate that the flame retardant properties of vegetable oil-based thermosets can be improved by adding covalently bonded phosphorus to the polymer.

      Corrected by:

      Erratum: Phospha-Michael addition to enone-containing triglyceride derivatives as an efficient route to flame retardant renewable thermosets

      Vol. 50, Issue 20, 4368, Article first published online: 5 JUL 2012

    22. Controlling the formation of long-subchain hyperbranched polystyrene from seesaw-type AB2 macromonomers: Solvent polarity and solubility (pages 3214–3224)

      Chen He, Wei-Dong He, Lian-Wei Li, Wen-Xing Jiang, Jing Tao, Jing Yang, Long Chen, Xue-Song Ge and Sheng-Qi Chen

      Article first published online: 28 APR 2012 | DOI: 10.1002/pola.26107

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      A series of long-chain hyperbranched polystyrene with high overall molar masses and regular subchain lengths were obtained. Comparing polycondensations of two seesaw macromonomers in two solvents, it was found that THF could restrict the self-cyclization of seesaw macromonomers and prompt the formation of hyperbranched polymers with high overall molar mass.

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