Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 7

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 3.245

ISI Journal Citation Reports © Ranking: 2013: 14/82 (Polymer Science)

Online ISSN: 1099-0518

Associated Title(s): Journal of Polymer Science Part B: Polymer Physics


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  1. Articles

    1. UV-responsive degradable polymers derived from 1-(4-aminophenyl) ethane-1,2-diol

      Liang Ma, Ryan Baumgartner, Yanfeng Zhang, Ziyuan Song, Kaimin Cai and Jianjun Cheng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27550

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      A UV-responsive polymer was prepared via condensation polymerization of 2-nitrobenzyl(4-(1,2-dihydroxyethyl)phenyl)carbamate and azalaic acid dichloride. Upon exposure to UV light, the nitrobenzyl urethane protecting group was removed and the deprotected aniline underwent spontaneous 1, 6-elimination reactions, resulting in degradation of the polymer. Nile Red was encapsulated in this novel degradable polymer nanoparticle by conventional emulsion method and triggered burst release of Nile Red was observed when the nanoparticles were irradiated by UV light.

    2. Synthesis of high thermal stability polybenzoxazoles via Ortho-imide-functional benzoxazine monomers

      Kan Zhang, Jia Liu, Seishi Ohashi, Xiaoyun Liu, Zhewen Han and Hatsuo Ishida

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27565

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      A series of imide functional benzoxazine resins were synthesized as precursors for producing cross-linked polyimide. In addition to polymerization of forming cross-linked polyimide, the ortho-imide functional benzoxazine resins can undergo a further smart route to form a more thermally stable cross-linked polybenzoxazole by releasing carbon dioxide. The ortho-imide functional benzoxazine resins show the possibility to form high performance thermosets with low cost and easy processability.

    3. Investigation of Suzuki–Miyaura catalyst-transfer polycondensation of AB-type fluorene monomer using coordination-saturated aryl Pd(II) halide complexes as initiators

      Zilong Zhang, Pan Hu, Xiao Li, Hongmei Zhan and Yanxiang Cheng

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27577

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      Stable aryl Pd(II) halide complexes with auxiliary ligands PCy3 and P(o-tol)3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors and achieved the catalyst-transfer polymerization to afford the well-defined polymers with triarylamine/H end groups. The complex with P(o-tol)3 has higher activity in the process of Suzuki–Miyaura catalyst-transfer polycondensation, which is comparable with the classical Pd(II) initiator ligated by P(tBu)3.

    4. Suppressing the long-chain branching in the synthesis of poly(styrene-b-butyl acrylate-b-styrene) in RAFT emulsion polymerization by tuning the interfacial properties

      Yunlong Guo, Xiang Gao and Yingwu Luo

      Article first published online: 27 FEB 2015 | DOI: 10.1002/pola.27578

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      In the synthesis of polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymer via reversible addition-fragmentation chain transfer emulsion polymerization, PDI is broadened by the formation of long-chain branches (LCBs) during the formation of the third block. Decreasing the interfacial transport resistance suppresses LCB formation, narrowing PDI.

    5. Effect of branched alkyl side chains on the performance of thin-film transistors and photovoltaic cells fabricated with isoindigo-based conjugated polymers

      Gi Eun Park, Jicheol Shin, Dae Hee Lee, Min Ju Cho and Dong Hoon Choi

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27555

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      New isoindigo and di(thienyl)ethylene-containing conjugated polymers with different branched side chains were successfully synthesized. PIDTE-S6 polymer bearing 11-heptyltricosane side chains showed much better charge transport behavior (µ = 4.07 cm2 V−1 s−1) than those of PIDTE-S3 with 11-butyltricosane side chains. In contrast, bulk heterojunction organic photovoltaic cells made from a blend film of PIDTE-S3 and PC61BM demonstrated promising device performance with a power conversion efficiency in the range of 4.9–5.0%.

    6. Preparation of photocrosslinked sol-gel composites based on urethane-acrylic matrix, silsesquioxane sequences, TiO2, and Ag/Au NPs for use in photocatalytic applications

      Andreea L. Chibac, Violeta Melinte, Tinca Buruiana, Ionel Mangalagiu and Emil C. Buruiana

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27548

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      The preparation of hybrid materials, incorporating titania and silsesquioxane units, achieved through the sol–gel and photopolymerization processes, together with photoinduced formation of noble metallic nanoparticles (Ag/Au) in polymer networks for eco-friendly photocatalysts, is reported.

    7. Base-amplifying silicone resins with photobase-generating side chains and their application to negative-working photoresists

      Masahiro Furutani, Hiroshi Kobayashi, Takahiro Gunji, Yoshimoto Abe and Koji Arimitsu

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27551

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      Functional silicone resins bearing both base-amplifying units and photobase-generating units to suppress excess diffusion of base species were designed. These resins are decomposed autocatalytically after UV irradiation and subsequent heating, which indicates progression of base-proliferation reactions. High photosensitivity is accomplished, and the sensitivity of the base-proliferation reaction system is about 490 times better than that of the corresponding base-catalytic reaction system. A 4 × 10 µm line-and-space pattern has also been fabricated.

    8. Amphiphilic pentablock copolymers and their blends with PDMS for antibiofouling coatings

      Elisa Martinelli, Elisa Guazzelli, Cristina Bartoli, Matteo Gazzarri, Federica Chiellini, Giancarlo Galli, Maureen E. Callow, James A. Callow, John A. Finlay and Sophie Hill

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27554

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      Novel amphiphilic ABCBA pentablock copolymers were synthesized via ATRP. The presence of a central siloxane block allowed for dispersion of the copolymers in a crosslinked PDMS matrix in various loadings. Inclusion of the copolymer in the PDMS-matrix coatings enhanced the HSA and calf serum protein adsorption and decreased the adhesion strength of the sporelings of fouling macroalga Ulva linza. Biological results point to a potential of these systems as fouling release coatings.

    9. pH and glucose dually responsive injectable hydrogel prepared by in situ crosslinking of phenylboronic modified chitosan and oxidized dextran

      Juan Li, Weiqiong Hu, Yajuan Zhang, Hui Tan, Xiaojun Yan, Lingling Zhao and Hongze Liang

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27556

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      pH and glucose dually responsive injectable hydrogels are synthesized based on biocompatible phenylboronic modified chitosan and oxide dextran, through the formation of a dynamic covalent imine bond and phenylboronate ester. Drugs and cells can be encapsulated inside the hydrogels through the in situ gel-forming process. Sustained and controlled drug release, and sensitive cell proliferation in the 3D hydrogel matrix are observed, showing potential applications of the system in biomedicine.

    10. Synthesis and polymerization of phenylacetylene having two carbazole units and properties of the formed polymer

      Natsuhiro Sano, Kazuki Banzai, Shigeki Naka, Hiroyuki Okada and Fumio Sanda

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27557

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      Novel carbazole-containing acetylene monomer 1 was synthesized, polymerized and copolymerized with phenylacetylene (PA). Polymers with number-average molecular weights ranging from 7800 to 33,200 were obtained in 60%–quantitative yields. The absorption band edge of poly(1-co-PA) (1PA = 8:2) was positioned at a wavelength longer than those of 1 and polyvinylcarbazole. The copolymer emitted fluorescence with 60% quantum yield, and worked as a hole transport material of an OLED.

  2. Rapid Communication

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      Detection and differentiation of ferrous and ferric ions using fluorescent metallopolymer and oligomer chemosensors

      Megan E. A. Fegley, Trevor Sandgren, Jetty L. Duffy-Matzner, Anting Chen and Wayne E. Jones Jr.

      Article first published online: 21 FEB 2015 | DOI: 10.1002/pola.27560

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      A new fluorescent conjugated oligimer, tmpda-PPETE, capable of selective and sensitive detection of Fe2+ relative to Fe3+ has been prepared and compared with previously characterized metallopolymerchemosensors. Metal cation titration showed significant quenching for Fe3+ ions and little interference in emission in the presence of other metal cations. This work establishes a new approach to modifying selectivity for PPETE turn-on and turn-off fluorescence sensors by varying chain lengths between nitrogen atoms of bidentate amino-based receptors.

  3. Articles

    1. Synthesis of ultra-small branched star poly(ε-caprolactone)s and their high end group concentration effects on crystallization

      Woohyuk Choi, Jae Woo Chung and Seung-Yeop Kwak

      Article first published online: 16 FEB 2015 | DOI: 10.1002/pola.27544

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      Ultra-small branched star poly(ε-caprolactone)s with well-defined architecture were successfully synthesized in high purity and high yield using a pilot-scale pseudo-one-pot process via manipulating monomer-to-core ratio, adjusting monomer-to-polymer conversion, end-capping the terminal hydroxyl groups, and vacuum purification. This synthetic protocol did not permit backbiting side reactions, enabling easy control over the molecular architectures of SPCLs, even with extremely small branches. They showed reduced crystallization and molecular weight-dependent glass transition due to the small size of the branches.

    2. Polyisobutylene-b-Poly(N,N-diethylacrylamide) well-defined amphiphilic diblock copolymer: Synthesis and thermo-responsive phase behavior

      Chunhong Ren, Xunwei Liu, Xue Jiang, Gang Sun and Xiaoyu Huang

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27545

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      This article reports the synthesis of polyisobutylene-b-poly(N,N-diethylacrylamide) well-defined amphiphilic thermo-responsive diblock copolymers via the combination of living carbocationic polymerization and RAFT polymerization.

  4. Rapid Communication

    1. Crosslinking of fluoroelastomers by “click” azide–nitrile cycloaddition

      Guillaume Tillet, Gérald Lopez, Ming-Hong Hung and Bruno Améduri

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27549

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      A fluoroelastomer that bears pendant nitrile groups is crosslinked with a telechelic bis-azido fluorinated curing agent by “click” azide–nitrile cycloaddition. Thermogravimetric analyses of the resulting press cured films reveal an improvement by 20 °C of the thermal degradation profile under air, compared to that of the corresponding uncured fluoroelastomer.

  5. Articles

    1. Amphiphilic thermoset elastomers from metal-free, click crosslinking of PEG-grafted silicone surfactants

      Talena Rambarran, Ferdinand Gonzaga, Michael A. Brook, Frances Lasowski and Heather Sheardown

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27539

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      Metal-free click reactions between azidoalkylsilicones, alkynyl-PDMS and alkynyl-PEGs lead readily to hydrophilic silicone elastomers. Monoalkynyl-functional PEGs were first clicked onto a fraction of the available azido groups of a functional polysiloxane backbone, yielding azido reactive PDMS-g-PEG rake surfactants. These polymers were then used to crosslink α,ω-alkynyl PDMS of different molecular weights. Using a few simple starting materials, this generic yet highly versatile method permits the preparation and characterization of a library of amphiphilic elastomers and hydrogels.

    2. Polyisobutylene containing organic/inorganic hybrid block copolymers and their crystalline behavior

      Ujjal Haldar, Kamal Bauri, Ren Li, Rudolf Faust and Priyadarsi De

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27543

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      The present study reveals the synthesis of novel block copolymers comprising of flexible PIB segment and rigid POSS segment by combination of carbocationic and reversible addition-fragmentation chain transfer (RAFT) polymerizations. PIB containing organic/inorganic hybrid block copolymers are able to induce crystalline properties, which lead to significant insights for development of superior composite materials towards materials chemistry.

    3. Star-shaped cyclopolymers: A new category of star polymer with rigid cyclized arms prepared by controlled cationic cyclopolymerization and subsequent microgel formation of divinyl ethers

      Tamotsu Hashimoto, Haruki Matsui, Michio Urushisaki and Toshikazu Sakaguchi

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27540

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      Star-shaped cyclopoly(divinyl ether)s with rigid cyclized arms [star-poly(1)] were synthesized by living/controlled cationic cyclopolymerization of 4,4-bis(vinyloxymethyl)-cyclohexene (1) and the subsequent chain linking reactions of the formed living cyclopolymers with 1,4-bis(vinyloxy)hexane as a crosslinker. Dihydroxylation of the cyclohexene double bonds of star-poly(1) gave hydrophilic water-soluble rigid star-shaped polymers [star-poly(1)-OH] with thermo-responsive function.

    4. Formation of thermo-sensitive and cross-linkable micelles by self-assembly of poly(pentafluorophenyl acrylate)-containing block copolymer

      Wilaiporn Graisuwan, Hui Zhao, Suda Kiatkamjornwong, Patrick Theato and Voravee P. Hoven

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27541

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      Amphiphilic poly(pentafluorophenyl acrylate)-block-poly(N-isopropylacrylamide) (PPFPA-b-PNIPAM) was synthesized by RAFT polymerization. Post-polymerization modification of the copolymer by ortho-nitrobenzyl (ONB) protected diamine thus yielded stable, core-cross-linked micelles upon self-assembly followed by UV irradiation. The ability to uptake active molecules, namely 4-nitro-7-piperazino-2,1,3-benzoxadiazole (NBD) and pyrene within the core of the micelles by tandem post-polymerization modification of the remaining PFPA groups and physical encapsulation, respectively has been highlighted to demonstrate their potential as thermo-sensitive cargos for advanced applications.

    5. Synthesis of poly(vinyl ether)-based, ABA triblock-type thermoplastic elastomers with functionalized soft segments and their gas permeability

      Tamotsu Hashimoto, Tsuguto Imaeda, Satoshi Irie, Michio Urushisaki and Toshikazu Sakaguchi

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27542

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      The poly(vinyl ether)-based, ABA-typed triblock copolymers consisting of poly(2-adamantyl vinyl ether) as outer hard segments and poly(6-acetoxyhexyl vinyl ether), poly(6-hydroxyhexyl vinyl ether), or poly(2-(2-methoxyethoxy)ethyl vinyl ether) as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxy, and oxyethylene units in their soft segments, the block copolymers formed elastomeric films. The effect on gas permeability of the functional groups in the soft segments was investigated.

    6. Synthesis, physicochemical characteristics, and biocompatibility of self-assemble polymers bearing guanine, cytosine, uracil, and thymine moieties

      Jin Chul Kim, Mihee Kim, Jungwoon Jung, Jinseok Lee, Brian J. Ree, Heesoo Kim, Ik Jung Kim, Jung Ran Kim and Moonhor Ree

      Article first published online: 7 FEB 2015 | DOI: 10.1002/pola.27546

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      Chemically well-defined brush polymers bearing guanine, cytosine, uracil, or thymine moieties at the bristle ends were synthesized. These polymers were thermally stable, and readily solution-processable, yielding high-quality films. They favorably self-assembled as molecular multibilayer structures, always providing nucleobase-rich surfaces. The multibilayer-structured polymer films showed water affinity and selective protein adsorption, suppressed bacterial adherence, facilitated cell adhesion, exhibited good biocompatibility in mice, and are suitable as biomaterials and in protein separation applications.

    7. Greatly enhanced thermo-oxidative stability of polybenzoxazine thermoset by incorporation of m-carborane

      Xin Huang, Qiuhong Zhang, Zheng Meng, Jiangjiang Gu, Xudong Jia and Kai Xi

      Article first published online: 3 FEB 2015 | DOI: 10.1002/pola.27525

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      A novel polybenzoxazine with high modulus and prominent thermo-oxidative stability under high temperature was prepared. The results demonstrate great promise for carborane-containing polybenzoxazines as a new generation of space-survivable materials.

    8. Syntheses of donor acceptor biobased photocurable water-soluble resins based on poly-l-lysine

      Houria Koleilat, Olivia Giani, Christine Joly-Duhamel and Jean-Jacques Robin

      Article first published online: 3 FEB 2015 | DOI: 10.1002/pola.27523

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      A novel biobased poly(aminoacid) resin is synthesized and the use in coating applications is demonstrated. Water-soluble oligomers of poly-L-lysine performed by thermal polymerization were transformed in mild conditions to give photocurable water-soluble resins. This new coating contributes to the development of materials based on renewable resources and more clean processes.

    9. Synthesis of tertiary amine-based pH-responsive polymers by RAFT Polymerization

      Liping Zhu, Samantha Powell and Stephen G. Boyes

      Article first published online: 3 FEB 2015 | DOI: 10.1002/pola.27529

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      Well-defined tertiary amine-based methacrylate pH-responsive homopolymers and block copolymers with a pKa of 5.1–6.8 have been prepared via RAFT polymerization using 4-cyanopentanoic acid dithiobenzoate (CPAD) as RAFT agent for homopolymers and poly(ethylene glycol) (PEG) macro-RAFT agents for block copolymers. A detailed study of the polymerization kinetics for each of these systems has been presented. Their pH-responsive properties studied by DLS justify their potential application in the diagnosis and treatment of cancer.

  6. Rapid Communication

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      “Metallophilic crosslinking” to provide fast-curing and mendable poly(urethane-metallothiolate) elastomers

      Alaitz Ruiz de Luzuriaga, Alaitz Rekondo, Roberto Martin, Germán Cabañero, Hans J. Grande and Ibon Odriozola

      Article first published online: 3 FEB 2015 | DOI: 10.1002/pola.27534

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      Thiol-functionalized liquid polyurethane is reacted with silver ions to obtain a supramolecular network stabilized by Ag–Ag metallophilic attractions.

  7. Articles

    1. Blue light-emitting hyperbranched polymers using fluorene-co-dibenzothiophene-S,S-dioxide as branches

      Ting Guo, Lei Yu, Baofeng Zhao, Lei Ying, Hongbin Wu, Wei Yang and Yong Cao

      Article first published online: 3 FEB 2015 | DOI: 10.1002/pola.27532

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      A series of hyperbranched polymers comprising poly(fluorene-co-dibenzothiophene-S,S-dioxide) as branches and benzene, triphenylamine, or triphenyltriazine as the core unit were synthesized. The resulted copolymers demonstrated efficient blue emission with the maximum luminous efficiency of 4.5 cd A−1 and excellent stability of electroluminescence.

    2. Molecular design of diene monomers containing an ester functional group for the synthesis of poly(diene sulfone)s by radical alternating copolymerization with sulfur dioxide

      Akikazu Matsumoto, Sungi Lee and Haruyuki Okamura

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27528

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      Functional poly(diene sulfone)s are synthesized by the alternating copolymerization of 1,3-diene monomers containing an ester substituent with sulfur dioxide as the comonomer and their thermal and optical properties are investigated. Methyl 3,5-hexadienoate (MH) and methyl 5,7-octadienoate (MO) with an alkylene spacer and a terminal diene structure produce a high-molecular-weight copolymer in a high yield. Fluorene-containing diene monomers, FH and FO, are also copolymerized to obtain copolymers with a high refractive index.

  8. Article

    1. Facile synthesis of linear–hyperbranched polyphosphoesters via one-pot tandem ROMP and ADMET polymerization and their transformation to architecturally defined nanoparticles

      Liang Ding, Ling Lin, Chengshuang Wang, Jun Qiu and Zhenshu Zhu

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27524

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      One-pot tandem ROMP and ADMET polymerization was successfully applied for the preparation of linear–hyperbranched polyphosphoesters (l–HBPPEs) bearing lots of pendent thiol groups in linear poly(norbornene) and peripheral acrylate groups in HBPPE, which could be self-crosslinked in ultradilute solution through thiol-Michael addition click reaction to fabricate the novel nanomaterials.

  9. Articles

    1. Homo-double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines

      Wataru Makiguchi, Shinzo Kobayashi, Keisuke Furukawa, Hiroki Iida, Yoshio Furusho and Eiji Yashima

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27527

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      An optically active π-conjugated polymer with carboxy groups formed a homo-double helix with an excess helical handedness through self-association. Upon complexation with achiral amines, the handedness excess of the duplex was further amplified via hydrogen-bonded inclusion complexation with the achiral amines between each strand.

    2. Iodonium-polyoxometalate and thianthrenium-polyoxometalate as new one-component UV photoinitiators for radical and cationic polymerization

      Haifaa Mokbel, Pu Xiao, Corine Simonnet-Jégat, Frederic Dumur, Didier Gigmes, Joumana Toufaily, Tayssir Hamieh, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27526

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      Four novel onium salts (onium-polyoxometalate) have been synthesized and characterized. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate as new counter anions. These novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively.

    3. Highly fluorescent polycaprolactones decorated with di(thiophene-2-yl)-diketopyrrolopyrrole: A covalent strategy of tuning fluorescence properties in solid states

      Kai Wang, Yimin Luo, Shuo Huang, Hongbin Yang, Bin Liu and Mingfeng Wang

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27531

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      1,4-Diketo-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole (DTDPP) labeled polycaprolactones (PCL) with different chain lengths are synthesized via ring-opening polymerization. The effect of polymer chain lengths on the optical properties of DTDPP in solid states indicates that when the PCL side chain is extended to a certain length, the intermolecular aggregation of DTDPP units can be reduced significantly due to segregation effect of PCL. This approach offers a new facile strategy to address the common aggregation-caused quenching problem for organic fluorophores.

    4. Synthesis, characterization, and properties of vinyl-terminated copolysiloxanes containing trifluoropropyl and 4-trifluoromethylphenyl groups

      Hua-Feng Fei, Xiyin Gao, Xiaojie Han, Qian Wang, Tao Hu, Zhijie Zhang and Zemin Xie

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27530

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      Novel copolysiloxanes with high thermal stability, outstanding damping properties and fuel resistance could be used as promising materials in view of their unique properties.

    5. Synthesis and properties of poly(thiourethane)s having soft oligoether segments

      Yukiko Inoue, Kozo Matsumoto and Takeshi Endo

      Article first published online: 1 FEB 2015 | DOI: 10.1002/pola.27535

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      Poly(thiourethane)s having soft oligoether segments were effectively synthesized by the polyaddition of bis(five-membered cyclic dithiocarbonate), 2,2-bis[4-(1,3-thioxolane-2-one-4-yl-methoxy)phenyl]propane, with α,ω-diaminooligoethers. The obtained polymers showed higher thermal stability than analogous polymers prepared from usual oligomethylene diamines.


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