Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 22

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

Impact Factor: 3.113

ISI Journal Citation Reports © Ranking: 2014: 18/82 (Polymer Science)

Online ISSN: 1099-0518

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


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  1. Articles

    1. Efficient and robust coatings using poly(2-methyl-2-oxazoline) and its copolymers for marine and bacterial fouling prevention

      Tao He, Dominik Jańczewski, Satyasankar Jana, Anbanandam Parthiban, Shifeng Guo, Xiaoying Zhu, Serina Siew-Chen Lee, Fernando Jose Parra-Velandia, Serena Lay-Ming Teo and G. Julius Vancso

      Article first published online: 7 OCT 2015 | DOI: 10.1002/pola.27912

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      Thin-film coatings based on PMOX and its copolymers with negative, neutral, and positive ζ-potential were investigated to tackle the problem of marine and bacterial fouling prevention. The coatings were stable in sea water for at least 1 month without significant reduction in the film thickness. Performance tests showed that PMOX coatings effectively reduced bacterial Staphylococcus aureus and Escherichia coli adhesion and possessed marine antifouling activity against barnacle cyprids Amphibalanus amphitrite and algae Amphora coffeaeformis.

    2. Synthesis of poly(isopropenylphenoxy propylene carbonate) and its facile side-chain functionalization into hydroxy-polyurethanes

      Chun Chieh Huang, Ching Hsuan Lin and Shenghong A. Dai

      Article first published online: 7 OCT 2015 | DOI: 10.1002/pola.27914

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      Synthesis of hydroxyl-polyurethanes through ring-opening reaction of cyclic carbonate with amines is a potentially useful green process without toxic isocyanates. In this study, a linear homo-polymer, poly(isopropenylphenoxy propylene carbonate), [poly (IPPC)] is prepared, possessing multi-cyclic carbonates on the side-chain through cationic polymerization of IPPC. Thus, curing of the poly(IPPC) with diamines readily resulted in the formation of hydroxyl-polyurethanes on the side-chain which were characterized by the initial soluble phase but then turned into the final insoluble crosslinked films upon solvent removal.

    3. N-bromo-hydantoin grafted polystyrene beads: Synthesis and nano-micro beads characteristics for achieving controlled release of active oxidative bromine and extended microbial inactivation efficiency

      Shady Farah, Oren Aviv, Mahran Daif, Konda Reddy Kunduru, Natalia Laout, Stanislav Ratner, Nurit Beyth and Abraham J. Domb

      Article first published online: 5 OCT 2015 | DOI: 10.1002/pola.27894

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      Chemically or kinetically release modified N-halamine hydantoins conjugated polystyrenes beads were studied. Beside chemical modifications, bead's nano-micro characteristics were found critical for oxidative halogen release control: rate stabilization and modulation, extension and also influences antimicrobial activity. Distinct controlled releasing profiles were found and extended strong antimicrobial activity for hundreds of liters. These parameters are important to explore, since the rate of halogen release influences antimicrobial activity and subsequently the material usage for different applications.

    4. “Grafting through” polymerization involving surface-bound monomers

      Preeta Datta and Jan Genzer

      Article first published online: 5 OCT 2015 | DOI: 10.1002/pola.27907

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      Snapshot from a typical simulation run showing two chains (red and blue) “grafted through” on the substrate. The substrate-bound monomers are depicted in darker hue of the same color. The dark grey spheres represent unused substrate-bound monomer units.

  2. Rapid Communication

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      Conjugated polymer with ternary electron-deficient units for ambipolar nanowire field-effect transistors

      Yunjing Ji, Chengyi Xiao, Gaël H. L. Heintges, Yonggang Wu, René A. J. Janssen, Deqing Zhang, Wenping Hu, Zhaohui Wang and Weiwei Li

      Article first published online: 5 OCT 2015 | DOI: 10.1002/pola.27898

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      A small band gap conjugated polymer with ternary acceptors of diketopyrrolopyrrole, benzothiadiazole, and naphthalenediimde is presented. Nanowires of this polymer were fabricated to show ambipolar field-effect transistors with hole and electron mobilities of 1.61 and 0.98 cm2 V−1 s−1.

  3. Articles

    1. Highly efficient water-soluble visible light photoinitiators

      Stephan Benedikt, Jieping Wang, Marica Markovic, Norbert Moszner, Kurt Dietliker, Aleksandr Ovsianikov, Hansjörg Grützmacher and Robert Liska

      Article first published online: 5 OCT 2015 | DOI: 10.1002/pola.27903

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      Environmental friendly photocurable formulations are widely used for water-borne coatings or hydrogel production for medicinal use. Currently there is a lack of suitable and commercially available photoinitiators with satisfying properties for such water-based formulations. In our article we describe efficient compounds based on acylphosphine oxide salts for visible light curing. These salts provide excellent solubility in water, cytocompatibility, good storage stability, and high reactivity.

    2. Supramolecular polymer gels from polystyrene bearing cyclic amidine Group and acrylic acid/n-butyl acrylate copolymers

      Mina Sakuragi, Naoto Aoyagi, Yoshio Furusho and Takeshi Endo

      Article first published online: 5 OCT 2015 | DOI: 10.1002/pola.27909

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      Supramolecular polymer gels were prepared from polystyrene bearing cyclic amidine pendant group and copolymers of acrylic acid and n-butyl acrylate. The gel formation was attributed to the three-dimensional network of the amidinium-carboxylate salt bridge. Dynamic shear measurements showed that the gel had G' higher than G" over a temperature range of −22 °C to 32 °C, where the G' value reached almost 1 MPa.

    3. Hole-buffer polymer composed of alternating p-terphenyl and tetraethylene glycol ether moieties: Synthesis and application in polymer light-emitting diodes

      Sheng-Ying Chou and Yun Chen

      Article first published online: 30 SEP 2015 | DOI: 10.1002/pola.27911

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      A new hole-buffer polymer 3P5O composed of alternating p-terphenyl and tetraethylene glycol ether segments has been synthesized and successfully applied in PLEDs to efficiently enhance device performance. The 3P5O is inserted between hole injection layer (PEDOT:PSS) and emission layer (Super Yellow) to diminish hole transport that leads to enhancing carrier recombination ratio and device efficiency.

    4. Cyclization and dispersity of poly(alkylene isophthalate)s

      Steffen M. Weidner, Hans R. Kricheldorf and Felix Scheliga

      Article first published online: 28 SEP 2015 | DOI: 10.1002/pola.27892

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      Two different methods were used to synthesize poly(alkylene isophthalate)s. In contrast to polymerizations in solution, where large fractions of rings were formed, polymers synthesized in bulk were almost free of cyclics. In either case higher polydispersities were obtained compared with theoretical values. The SEC data obtained in two solvents and from different laboratories were compared with each other, and with data from universal calibration, showing a significant discrepancy.

    5. Electrochemical procedure for constructing poly(phenylene sulfide) brushes on glassy carbon and stainless steel

      Kyoko Shimizu, Frances Helen Blaikie, Mikkel Kongsfelt, Kristian Damgaard Schøler Sørensen, Steen Uttrup Pedersen and Kim Daasbjerg

      Article first published online: 28 SEP 2015 | DOI: 10.1002/pola.27893

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      Poly(phenylene sulfide) brushes on glassy carbon and stainless steel are constructed from 4,4’-disulfanediyldibenzenediazonium salt using potential sweeping. Exact control on the brush length may be exerted through the switching potential selected or the number of sweeps applied. The films are characterized by means of cyclic voltammetry, ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and Raman spectroscopy.

    6. Organocatalytic synthesis of novel renewable non-isocyanate polyhydroxyurethanes

      Charlotte Duval, Nasreddine Kébir, Raphaël Jauseau and Fabrice Burel

      Article first published online: 28 SEP 2015 | DOI: 10.1002/pola.27908

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      Novel fully renewable polyhydroxyurethanes are prepared from sebacic acid, glycerol carbonate, and diamines.

  4. Rapid Communications

    1. Synthesis and radical ring-opening polymerization of adamantane-containing bifunctional vinylcyclopropane undergoing volume expansion on polymerization

      Hiroto Chiba, Koji Kitazume, Shuhei Yamada and Takeshi Endo

      Article first published online: 26 SEP 2015 | DOI: 10.1002/pola.27904

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      We describe the synthesis and radical ring-opening polymerization of an adamantane-substituted bifunctional vinylcyclopropane monomer. The radical polymerization using AIBN as a radical initiator proceeded smoothly at 60 °C along with a large volume expansion (+6.1%) to afford the corresponding networked polymer. The structural analysis with the solid-state 13C NMR clearly revealed that radical polymerization occurred predominantly by a 1,5 ring-opened reaction. Furthermore, copolymerization of bifunctional methacrylate monomer with the vinylcyclopropane monomer provided controlled volume shrinkage by varying the feeding ratio.

  5. Articles

    1. Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10,11-didehydrogenated cinchonidinium salt

      Md. Mehadi Hassan, Naoki Haraguchi and Shinichi Itsuno

      Article first published online: 26 SEP 2015 | DOI: 10.1002/pola.27905

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      Dimers of 10,11-didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N-(diphenylmethylen)glycine tert-butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity.

    2. Visible light-induced thiol-ene reaction: A new strategy to prepare Α,ω-dithiol and Α,ω-divinyl telechelic polythiolether oligomers

      Wenchao Ma, Dong Chen, Lianying Liu, Yuhong Ma, Li Wang, Changwen Zhao and Wantai Yang

      Article first published online: 26 SEP 2015 | DOI: 10.1002/pola.27906

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      Both α,ω-dithiol- and α,ω-divinyl-terminated linear polythiolether oligomers are obtained by visible light induced thiol-ene chemistry in the presence of a fac-Ir(ppy)3 photoredox catalyst. Thereafter, well-defined polymer (Mn=7700 g mol−1, PDI=1.67) is obtained by polyaddition of α,ω-dithiol- (Mn=1900 g mol−1, PDI=1.25) and α,ω-divinyl-terminated (Mn=2000 g mol−1, PDI=1.29) oligomers. The results demonstrate that as-prepared α,ω-dithiol and α,ω-divinyl linear telechelic polythiolether oligomers possess high end-group fidelity.

    3. Comparative study on post-polymerization modification of C1 poly(benzyl 2-ylidene-acetate) and its C2 analog poly(benzyl acrylate)

      Tim Krappitz and Patrick Theato

      Article first published online: 25 SEP 2015 | DOI: 10.1002/pola.27891

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      Post-polymerization modification of C1 polymers, obtained from polymerization of carbene precursors, and C2 polymers, obtained from classic radical polymerization of functional acrylates, result in different products during amidation reactions. This was tested for bulk reaction of non-activated ester polymers with amines.

    4. Iron complexes as potential photocatalysts for controlled radical photopolymerizations: A tool for modifications and patterning of surfaces

      Sofia Telitel, Frederic Dumur, Damien Campolo, Julien Poly, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 25 SEP 2015 | DOI: 10.1002/pola.27896

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      In this article, radical polymerization reactions can be efficiently carried out using novel photoinitiating systems (PIS) based on iron complexes (e.g., FeC1) using a photoredox catalytic cycle. Re-initiation experiments under light allow the synthesis of copolymers [e.g., poly(MMA)-b-poly(BA)]. Although the reported (FeC1/amine/RBr) does not give the control that is observed for other reported catalysts, the presence of dormant species that can re-initiate a polymerization on-demand upon soft irradiation conditions can be very valuable for surface modification or surface patterning purposes.

    5. Di-nuclear zinc complexes containing tridentate imino-benzotriazole phenolate derivatives as efficient catalysts for ring-opening polymerization of cyclic esters and copolymerization of phthalic anhydride with cyclohexene oxide

      Chin-Hsiang Chang, Hui-Ju Chuang, Ting-Yi Chen, Chen-Yu Li, Chia-Her Lin, Ting-Yu Lee, Bao-Tsan Ko and Hsi-Ya Huang

      Article first published online: 25 SEP 2015 | DOI: 10.1002/pola.27902

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      New imino-benzotriazole phenolate (IBTP) zinc complexes were synthesized for versatile catalysis of ring-opening polymerization (ROP) and copolymerization of epoxide with cyclic anhydride. Di-nuclear IBTP-ligated Zn complex 1 was demonstrated to efficiently catalyze not only ROP of cyclic esters but also copolymerization of cyclohexene oxide and phthalic anhydride. In combination with 9-anthracenemethanol (9-AnOH), Zn catalyst 1 was found to polymerize ε-CL, β-BL and L-LA with effective catalytic activities in a controlled character.

    6. Amphiphilic β-cyclodextrin-based star-like block copolymer unimolecular micelles for facile in situ preparation of gold nanoparticles

      Na Yao, Wenjing Lin, Xiaofang Zhang, Huawei Gu and Lijuan Zhang

      Article first published online: 23 SEP 2015 | DOI: 10.1002/pola.27889

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      The β-CD-(PLA-PDMAEMA-PEtOxMA)21 unimolecullar micelles are promising stabilizers and reductants for the preparation of gold nanoparticles owing to the tertiary amine groups of DMAEMA can reduce the AuCl4- counterion to zerovalent gold in situ and then grow to final gold nanoparticles, which is attractive for further biological application.

  6. Highlights

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      Tailoring block copolymer and polymer blend morphology using nanoparticle surfactants

      Kang Hee Ku, Hyunseung Yang, Se Gyu Jang, Joona Bang and Bumjoon J. Kim

      Article first published online: 23 SEP 2015 | DOI: 10.1002/pola.27899

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      In this review, recent investigations of the assembly of size- and shape-controlled nanoparticle (NP) surfactants at the polymer/polymer interface and at the surface of the block copolymer (BCP) emulsion droplets were discussed. Novel nanostructures driven by NP surfactants for BCP and polymer blend morphologies and BCP emulsion particles were described. The introduction of NPs with controlled surface chemistry and shape will provide a powerful and efficient strategy for modifying the interfacial properties of the polymers toward the fabrication of next generation novel structured materials.

  7. Articles

    1. Controlled synthesis of amphiphilic block copolymers based on poly(isobutylene) macromonomers

      Edward L. Malins, Carl Waterson and C. Remzi Becer

      Article first published online: 21 SEP 2015 | DOI: 10.1002/pola.27812

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      Polyisobutylene (PIB) containing polymers have a great commercial importance in various fields. Converting a commercially available PIB into a polymerizable PIB macromonomer allows the synthesis of amphiphilic block copolymers via RAFT polymerization. The chain length and block ratios of PIB and acrylamide comonomers can be tuned using appropriate reaction conditions.

    2. Donor–acceptor-structured naphtodithiophene-based copolymers for organic thin-film transistors

      Myeong-Jong Kim, Ye Seul Lee, Sung Chul Shin and Yun-Hi Kim

      Article first published online: 21 SEP 2015 | DOI: 10.1002/pola.27803

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      New D-A type copolymers, composed of naphto[2,1-b:3,4-b′]dithiophene and benzothiadiazole were designed and synthesized for use in high-performance solution-processed OTFTs. Poly(4,5-bis(2-octyldodecyloxy)naphto[2,1-b:3,4-b′]dithiophene-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole) with linker groups had high crystallinity and high mobility.

  8. Original Articles

    1. Synthesis of diblock copolymers by combination of organocatalyzed ring-opening polymerization and atom transfer radical polymerization using trichloroethanol as a bifunctional initiator

      Victoria A. Piunova, Hans W. Horn, Gavin O. Jones, Julia E. Rice and Robert D. Miller

      Article first published online: 17 SEP 2015 | DOI: 10.1002/pola.27807

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      Trichloroethanol (TCE) was employed for the synthesis of block copolymers (BCPs) by the combination of organocatalyzed ring-opening polymerization and atom transfer radical polymerization. The formation of well-defined BCPs was confirmed by gel permeation chromatography and 1H NMR. Computational studies were performed to obtain a molecular-level understanding of the ring-opening polymerization mechanism involving TCE as initiator.

  9. Articles

    1. The effect of irradiation by ultraviolet light on ureido-pyrimidinone based biomaterials

      Björne B. Mollet, Yoko Nakano, Pieter C. M. M. Magusin, A. J. H. Spiering, Jef A. J. M. Vekemans, Patricia Y. W. Dankers and E. W. Meijer

      Article first published online: 16 SEP 2015 | DOI: 10.1002/pola.27887

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      UV-irradiation used for sterilization of materials in medical applications, induces changes in ureido-pyrimidinone moieties in the form of crosslinking and fluorescence. The latter is related to a tautomeric shift from keto to enol, which is hypothesized to occur via photoinduced intermolecular double proton transfer. The identification and understanding of changes in dynamic UPy-materials is important for their controlled application, such as in biomaterials for tissue engineering application.

    2. Antibacterial poly(ethylene glycol) hydrogels from combined epoxy-amine and thiol-ene click reaction

      Chao Zhou, Vinh X. Truong, Yue Qu, Trevor Lithgow, Guodong Fu and John S. Forsythe

      Article first published online: 16 SEP 2015 | DOI: 10.1002/pola.27886

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      Antibacterial PEG hydrogels prepared from epoxy-amine ring opening reaction and thiol-ene click chemistry containing quaternary ammonium groups effectively inhibited S. aureus bacteria growth and biofilm formation.

    3. Synthesis and photovoltaic properties of two-dimensional copolymers based on novel benzothiadiazole and quinoxaline acceptors with conjugated dithienylbenzothiadiazole pendants

      Yuanshuai Huang, Linglong Ye, Fen Wu, Suli Mei, Huajie Chen and Songting Tan

      Article first published online: 16 SEP 2015 | DOI: 10.1002/pola.27888

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      Two novel conjugated polymers containning benzo[c][1,2,5]thiadiazole and quinoxaline with dithienylbenzothiadiazole pendant as acceptor units were synthesized and applied in polymer solar cells.

    4. Fully transparent nonvolatile resistive polymer memory

      Hwan-Chul Yu, Moon Young Kim, Jeong-Sup Lee, Kwang-Hun Lee, Kyoung Koo Baeck, Kyoung-Kook Kim, Soohaeng Cho and Chan-Moon Chung

      Article first published online: 16 SEP 2015 | DOI: 10.1002/pola.27897

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      A fully transparent nonvolatile resistive memory device derived from an anthracene-containing partially aliphatic polyimide along with ITO top and bottom electrodes is presented. A transmittance of over 90% in the wavelength range of 400 to 800 nm is accomplished with the ITO/polyimide/ITO/glass structure. The memory behavior of the device is considered to be governed by trap-controlled space-charge limited conduction and local filament formation.

    5. Novel ABC miktoarm star terpolyphosphoesters: Facile construction and high-flame retardant property

      Jun Qiu, Jiawen Zhang, Fangli Yu, Jun Wei and Liang Ding

      Article first published online: 15 SEP 2015 | DOI: 10.1002/pola.27895

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      Novel ABC miktoarm star terpolyphosphoesters were first obtained by a combination of ring-opening metathesis polymerization, ring-opening polymerization, and acyclic diene metathesis polymerization approach, which demonstrated superior thermal stability with a higher decomposition temperature and good flame retardant properties with a higher residual char mass.

    6. Polystyrene-b-poly(2,2,2-trifluoroethyl acrylate)-b-polystyrene copolymers: Synthesis and fabrication of their hydrophobic porous films, spheres, and fibers

      Chi Lv, Kun Cui, Shu-Cai Li, Hao-Tian Wu and Zhi Ma

      Article first published online: 15 SEP 2015 | DOI: 10.1002/pola.27890

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      New polystyrene-b-poly(2,2,2-trifluoroethyl acrylate)-b-polystyrene (PS-PTFEA-PS) triblock copolymers were successfully synthesized via a sequential RAFT polymerization. The porous films of PS-PTFEA-PS fabricated by static breath-figure process exhibited a good hydrophobicity with the water-droplet contact angle of 129°. In addition, the spheres and fibers of PS-PTFEA-PS were fabricated by an electrospinning process. The fibers showed higher hydrophobicity with the water-droplet contact angle of 142°.

    7. Thio-bromo “Click,” post-polymerization strategy for functionalizing ring opening metathesis polymerization (ROMP)-derived materials

      Venkata Ashok Kothapalli, Manasa Shetty, Christopher de los Santos and Christopher E. Hobbs

      Article first published online: 10 SEP 2015 | DOI: 10.1002/pola.27801

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      A facile nucleophilic substitution between thiols and α-bromo esters (thio-bromo “click” reaction) was used for the postpolymerization modification of ROMP-based materials. This metal-free click approach allowed for a multiple functional groups to be installed in a one-step, one-pot process, providing reactions in high yields. This could also be applied toward the preparation of polymeric gels as well as terminally functionalized polyolefins.

    8. Electrosynthesis of ambipolar electrochromic polymer films from anthraquinone–triarylamine hybrids

      Sheng-Huei Hsiao and Jhe-Yong Lin

      Article first published online: 4 SEP 2015 | DOI: 10.1002/pola.27813

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      This work describes the synthesis and electrochemical properties of two electropolymerizable monomers, AQ(TPA)2 and AQ(Cz)2, featuring an interior anthraquinone (AQ) segment bridged by benzoyloxy units to terminal electroactive carbazole and diphenylamino groups. The electron-deficient AQ groups efficiently blocked the radical cations delocalization between the two triphenylamino or carbazole groups, rendering the electropolymerization of the triphenylamino or carbazole groups feasible. The electrogenerated polymer films exhibited ambipolar electrochemical processes and obvious color changes upon electro-oxidation or electro-reduction, which can be switched by potential modulation.

  10. Rapid Communication

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      Investigation of intricate, amphiphilic crosslinked hyperbranched fluoropolymers as anti-icing coatings for extreme environments

      Jennifer S. Zigmond, Kevin A. Pollack, Sarah Smedley, Jeffery E. Raymond, Lauren A. Link, Adriana Pavía-Sanders, Michael A. Hickner and Karen L. Wooley

      Article first published online: 3 SEP 2015 | DOI: 10.1002/pola.27800

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      An array of films composed of a third-generation hyperbranched fluoropolymer crosslinked with poly(ethylene glycol) is generated and tested as an anti-icing coating. Through variation of the hydrophilic:hydrophobic component ratios and drop-casting solvent, significant reductions in the water melting transition temperatures (−5 and −27 °C for free and bound water, respectively) are achieved. The novel application of this system displays the expansion and diversity of a well-established coating that demonstrates unique water confinement and sequestration behaviors with the ability to reorganize at the surface.

  11. Original Articles

    1. Single component transparent free-standing films based on polyhedral octasilicate-core dendrimers bearing carbazole terminal groups and their emission properties

      Yasuyuki Irie and Kensuke Naka

      Article first published online: 3 SEP 2015 | DOI: 10.1002/pola.27811

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      Single Component Transparent Free-Standing Films Based on Polyhedral Octasilicate-Core Dendrimers Bearing Carbazole Terminal Groups and Their Emission Properties 9H-carbazole-9-ethyl and 9H-carbazole-9-hexyl-terminated polyhedral octasilicate (OS)-core dendrimers, denoted as OS-C2-Cz and OS-C6-Cz, respectively, were prepared and studied their bulk properties. Both the dedrimers formed optical transparent coating films. In particular, the coating film of OS-C2-Cz was easily peeled off from a substrate and formed a free-standing film. Photoluminescence property revealed that the carbazole group in OS-C2-Cz is prevented the excimer formation, while the carbazole group in OS-C6-Cz formed the excimer.

  12. Articles

    1. Continuous flow synthesis of poly(methyl methacrylate) via a light-mediated controlled radical polymerization

      Anna Melker, Brett P. Fors, Craig J. Hawker and Justin E. Poelma

      Article first published online: 29 AUG 2015 | DOI: 10.1002/pola.27765

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      Recently, the ability to control polymerizations using external stimuli such as light has gained attention. However, scaling up these reactions presents unique challenges such as shallow and uneven penetration of light through the reaction medium, effectively lowering the rate of polymerization. To circumvent these issues, a continuous flow reactor was used with special attention made to choice of tubing material, yielding 50% faster reaction rates compared to batch reactions.

    2. Polyisobutylene-based polyurethanes: VII. structure/property investigations for medical applications

      Kalman Toth, Nihan Nugay and Joseph P. Kennedy

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27804

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      The hydrolytic, oxidative, and metal ion oxidative resistance of PIB-based polyurethane is far superior to that of PDMS-based commercial polyurethane (Elast-Eon™ E2A), while their static mechanical properties (tensile strength and elongation) are comparable.

    3. High molecular weight and low dispersity polyacrylonitrile by low temperature RAFT polymerization

      Jeremy D. Moskowitz, Brooks A. Abel, Charles L. McCormick and Jeffrey S. Wiggins

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27806

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      Well-controlled polymers with uniform dispersity and high molecular weight serve as excellent model precursors for further study of in situ carbon fiber production of PAN-based carbon fibers. Well-controlled high molecular weight and low dispersity polyacrylonitrile (PAN) was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Through low temperature (30 °C) RAFT polymerization, chain termination and chain transfer reactions were suppressed leading to improved control, higher molecular weight PAN, and higher conversions.

    4. Effect of multiple H-bonding on the properties of polyimides containing the rigid rod groups

      Xiaoye Ma, Chuanqing Kang, Wenhui Chen, Rizhe Jin, Haiquan Guo, Xuepeng Qiu and Lianxun Gao

      Article first published online: 28 AUG 2015 | DOI: 10.1002/pola.27808

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      Five fully symmetrical diamines containing benzimidazole, benzoxazole, and hydroxyl group were synthesized and a series of polyimides were prepared by the reaction of these diamines with commercial aromatic dianhydrides. The influence on the properties of PIs by the introduction of rigid rod-like nitrogen heterocyclic structure and the formation of intra-/intermolecular H-bonding has been discussed.

    5. Radical polymerization behavior and molecular weight development of homologous monoacrylate monomers in lyotropic liquid crystal phases

      Michael A. DePierro, Céline Baguenard and C. Allan Guymon

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27783

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      Surfactant self-assembly can generate lyotropic liquid-crystalline mesophases such as hexagonal, bicontinuous cubic, or lamellar nanostructures. These geometries can be used as a photopolymerization template to synthesize materials with nanoscale features. Rapid radical polymerization kinetics and thermodynamics are key factors to better control nanostructure retention. Herein, monomer polarity, light intensity, and template geometry are correlated to the evolution of polymer molecular weight and radical photopolymerization kinetics to better understand the parameters that can improve the nanostructure transfer.

    6. Synthesis of poly(n-butyl acrylate) homopolymer and poly(styrene-b-n-butyl acrylate-b-styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

      Zhigang Xue, Zhen Wang, Dan He, Xingping Zhou and Xiaolin Xie

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27809

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      The AGET emulsion ATRPs using cationic surfactants are reported. Most of the systems showed the typical features of controlled radical polymerization.

    7. Homopolymerization and copolymerization kinetics of trimethylene carbonate bearing a methoxyethoxy side group

      Fei Chen and Brian G. Amsden

      Article first published online: 27 AUG 2015 | DOI: 10.1002/pola.27805

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      The homo- and copolymerization kinetics of a functional cyclic carbonate monomer bearing a methoxyethoxy pendant group (TMCM-MOE3OM) was investigated using the organocatalyst DBU as well as metal catalyst Sn(Oct)2. Compared with non-functionalized TMC as well as LLA, ring-chain equilibrium and autopolymerization were observed in the polymerization of TMCM-MOE3OM with either catalyst. This equilibrium along with autopolymeriation resulted in the formation of oligomers with Mn lower than 5000 Da.

    8. Sulfonated dendrimer- and hyperbranched polyglycerol-PBIOO® blend membranes for fuel cells

      Manuela Martín-Zarco, Joaquín C. García-Martínez and Julián Rodríguez-López

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27777

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      Acid-base proton-conducting membranes were prepared by blending either a new sulfonated dendrimer or different sulfonated hyperbranched polyglycerols with PBIOO®. Proton exchange capacity, water uptake, thermal stability, and proton conductivity were strongly dependent on the molecular structure and the microphase separation in the membranes.

    9. Synthesis and photovoltaic properties of 2,6-bis(2-thienyl) benzobisazole and 4,8-bis(thienyl)-benzo[1,2-B:4,5-B′]dithiophene copolymers

      Achala Bhuwalka, Monique D. Ewan, Moneim Elshobaki, Jared F. Mike, Brian Tlach, Sumit Chaudhary and Malika Jeffries-EL

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27793

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      Three donor–acceptor copolymers based on a donor–acceptor–donor triad of cis-benzbisoxazole, trans-benzobisoxazole, or trans-benzobisthiazole, and 4,8-bis(5-(2-ethylhexyl)-thien-2-yl)-benzo[1,2-b:4,5-b′]dithiophene were synthesized and the impact of these structural modifications the optical, electrochemical, and morphological properties of the polymers investigated. The performance of these copolymers in photovoltaic cells is also reported.

    10. Synthesis of an esterase-sensitive degradable polyester as facile drug carrier for cancer therapy

      Zhuxian Zhou, William J. Murdoch and Youqing Shen

      Article first published online: 22 AUG 2015 | DOI: 10.1002/pola.27798

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      The esterase-sensitive degradable polyether-based drug carrier (PEGx) was synthesized by polycondensation of PEG400 and dianhydride (A) following with conjugation of PEG2000 (B). Anticancer drugs were loaded by covalent conjugation through multiple carboxyl acid groups on PEGx and this polymer drug conjugates exhibited esterase-promoted degradation and drug release (C).

    11. Synthesis and characterization of new low band-gap polymers containing electron-accepting acenaphtho[1,2-c]thiophene-S,S-dioxide groups

      Yu-Rim Shin, Woo-Hyung Lee, Jong Baek Park, Ji-Hoon Kim, Sang Kyu Lee, Won Suk Shin, Do-Hoon Hwang and In-Nam Kang

      Article first published online: 21 AUG 2015 | DOI: 10.1002/pola.27797

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      Syntheses and characterization of two new acenaphthothiophene-S, S-dioxide (TSSO-based donor–acceptor polymers were described. The incorporation of TSSO units in these D–A polymers reduces their optical band-gap and HOMO/LUMO energy levels to produce a low band-gap polymer, which indicates the TSSO unit acts as a good electron-accepting unit in D–A donor polymer systems.

    12. End-functionalized polylactides using a calcium-based precatalyst: Synthesis and insights by mass spectrometry

      Ilknur Yildirim, Sarah Crotty, Claas H. Loh, Grit Festag, Christine Weber, Pier-Francesco Caponi, Michael Gottschaldt, Matthias Westerhausen and Ulrich S. Schubert

      Article first published online: 21 AUG 2015 | DOI: 10.1002/pola.27795

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      End-functionalized PLAs via ring opening polymerization of l-lactide were synthesized with heavy metal free catalysis. A variety of alcohols was used as initiator precursors like primary, secondary as well as tertiary alcohols. This enabled the direct introduction of targeting moieties, a drug molecule, a fluorescent label and a raft agent. All PLAs have been intensively investigated by mass spectrometry besides SEC and NMR spectroscopy.

    13. A route toward multifunctional polyurethanes using triple click reactions

      Erhan Demirel, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27796

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      The aliphatic polyurethane, with pendant alkyne, perfluorophenyl, and anthracene moieties, was prepared from polycondensation of anthracene, alkyne, and perfluorophenyl functional-diols with hexamethylenediisocyanate in the presence of dibutyltindilaurate in CH2Cl2 at room temperature for 10 days. Thereafter, the PU-(anthracene-co-alkyne-co-perfluorophenyl) (Mn,GPC = 15,600 g/mol, Mw/Mn = 1.37, relative to PS standards) was sequentially clicked with benzyl azide, octylamine, and 4-(2-hydroxyethyl)−10-oxa-4-azatricyclo[,6]dec-8-ene-3,5-dione (adduct alcohol) via copper-catalyzed azide-alkyne cycloaddition, active ester substitution, and Diels–Alder reactions, respectively, to finally yield PU-(hydroxyl-co-benzyltriazole-co-octylamine).

    14. Synthesis of poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

      Haotian Wu, Tao Jiang, Jun Zhu, Kun Cui, Qiaoling Zhao and Zhi Ma

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27799

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      A series of poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymers (EVAL-g-PS) were synthesized via the combination of the hydrolysis of poly(ethylene-co-vinyl acetate), the transformation of hydroxyl on the side chain through esterification and the ATRP of polystyrene. The applications of the copolymers in fabricating ordered porous films and compatibilizer for the blend system of low-density polyethylene/polystyrene are observed by SEM.

    15. Silicon-based mercaptans: High-performance monomers for thiol-ene photopolymerization

      Meinhart Roth, Andreas Oesterreicher, Florian H. Mostegel, Andreas Moser, Gerald Pinter, Matthias Edler, Richard Piock and Thomas Griesser

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27792

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      Ester-free silicon-based thiol monomers were successfully synthesized and evaluated for an application in thiol-ene resins. Polymerization reaction rates, conversion, network properties, shelf-life as well as degradation experiments of those thiol monomers in combination with triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione were performed and compared with formulations containing pentaerythritol tetra-3-mercaptopropionate. Kinetic analysis revealed appropriate reaction rates and conversions reaching 90% and higher. The excellent degradation resistance of photocured silane-based formulations makes these multifunctional mercaptans interesting candidates for high-performance applications.

    16. Novel reversible thermoresponsive nanogel based on poly(ionic liquid)s prepared via RAFT crosslinking copolymerization

      Yong Zuo, Na Guo, Zhenqian Jiao, Pengfei Song, Xiaojun Liu, Rongmin Wang and Yubing Xiong

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27789

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      In this study, a facile strategy for the preparation of thermo- and pH-responsive nanogels based on ionic liquids is fabricated through the reversible addition-fragmentation transfer (RAFT) cross-linking copolymerization in selective solvents. The use of chain transfer agents containing carboxyl groups in the RAFT polymerizations is the key to producing highly thermoresponsive nanogels. Furthermore, these nanogels can be further decorated via surface-grafting polymerization.

    17. Allyl sulfides and α-substituted acrylates as addition–fragmentation chain transfer agents for methacrylate polymer networks

      Samuel Clark Ligon, Konstanze Seidler, Christian Gorsche, Markus Griesser, Norbert Moszner and Robert Liska

      Article first published online: 17 AUG 2015 | DOI: 10.1002/pola.27788

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      Allyl sulfide and α-substituted acrylate based addition–fragmentation chain transfer agents can effectively modify the rate of gelation of multifunctional methacrylate monomers. Shrinkage stress is reduced and mechanical properties of the resultant network are positively influenced.

  13. Highlights

    1. Copper and iron complexes as visible-light-sensitive photoinitiators of polymerization

      Pu Xiao, Jing Zhang, Damien Campolo, Frederic Dumur, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 14 AUG 2015 | DOI: 10.1002/pola.27762

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      Copper or iron complexes with well-designed ligands can be utilized as photoinitiators of various polymerization reactions such as free radical photopolymerization, cationic photopolymerization, thiol-ene photopolymerization, and controlled radical photopolymerization under irradiation of visible light. The high efficiency and low cost of these complexes may endow them with potential applications in fabrication of polymer materials in green chemistry circumstance.

  14. Articles

    1. In situ fabrication of paclitaxel-loaded core-crosslinked micelles via thiol-ene “click” chemistry for reduction-responsive drug release

      Ying Huang, Rui Sun, Qiaojie Luo, Ying Wang, Kai Zhang, Xuliang Deng, Weipu Zhu, Xiaodong Li and Zhiquan Shen

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27778

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      A facile method to fabricate reduction-responsive core-crosslinked paclitaxel-loaded micelles via in situ thiolene “click” reaction is reported. These micelles could quickly release paclitaxel in response to high glutathione concentration in tumor cells.

    2. Efficient water-soluble drag reducing star polymers with improved mechanical stability

      David P. Cole, Ezat Khosravi and Osama M. Musa

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27779

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      The addition of high-molecular-weight polymers have been shown to greatly reduce the drag experienced by a fluid as it moves through a pipe. These polymers are highly susceptible to mechanical degradation in pipe flow, reducing their efficacy. This work here describes the synthesis of water soluble high-molecular-weight 4-arm star polymers via Cu(0)-mediated controlled radical polymerization. These star polymers demonstrated greatly enhanced mechanical stability in comparison with the currently used commercial polymers.

    3. Synthesis and FET characterization of novel ambipolar and low-bandgap naphthalene-diimide-based semiconducting polymers

      Seijiro Fukuta, Hung-Chin Wu, Tomoyuki Koganezawa, Yukou Isshiki, Mitsuru Ueda, Wen-Chang Chen and Tomoya Higashihara

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27782

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      Naphthalene-diimide-based semiconducting polymers (P1–P4) were synthesized for ambipolar semiconducting materials with near infra-red absorption. The introduction of the thiophene spacer and strongly electron-donating unit successfully extended the absorption peaks up to 1066 nm. P4 showed high electron mobility of 1.5 × 10−2 cmV−1 s−1 and moderate hole mobility of 2.9 × 10−4 cmV−1 s−1.

    4. New alternating D–A1–D–A2 copolymer containing two electron-deficient moieties based on benzothiadiazole and 9-(2-Octyldodecyl)-8H-pyrrolo[3,4-b]bisthieno[2,3-f:3',2'-h]quinoxaline-8,10(9H)-dione for efficient polymer solar cells

      M. L. Keshtov, S. A. Kuklin, D. Y. Godovsky, A. R. Khokhlov, R. Kurchania, F. C. Chen, Emmanuel N. Koukaras and G. D. Sharma

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27786

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      A novel D–A1–D–A2 copolymer P1 containing two electron withdrawing units based on benzothiadiazole (BT) and 9-(2-octyldodecyl)−8H-pyrrolo[3,4-b] bisthieno[2,3-f:3′, 2′-h]quinoxaline-8,10(9H)-dione (PTQD) units was synthesized and used as donor for the fabrication of bulk heterojunction polymer solar cells. The polymer solar cell with optimized P1:PC71BM active layer processed with DIO/CB showed power conversion efficiency of 6.21%.

    5. Synthesis of well-defined star-shaped poly(ε-caprolactone)/poly(ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry

      Cui-Wei Wang, Chao Liu, Xiao-Wei Zhu, Zi-Ying Yang, Hong-Fan Sun, De-Ling Kong and Jing Yang

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27790

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      Star-shaped PCL-PEG amphiphilic conetworks (APCNs) have been synthesized via the combination of ring opening polymerization (ROP) and click chemistry. The APCNs showed different swelling behaviors in different solvent. Furthermore, by in vitro release of hydrophobic and hydrophilic drugs, the APCNs was confirmed to be promising drug depot materials for the hydrophobic and hydrophilic drugs.

  15. Rapid Communication

    1. You have free access to this content
      Hydrothermal synthesis of aromatic polyimide particles by using reaction-induced crystallization

      Daisaku Shojo, Shinichi Yamazaki and Kunio Kimura

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27791

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      Highly crystalline poly(p-phenylene pyromellitimide) plate-like crystals were obtained in water at 280 °C only for 10 min by the combination of the crystallization of oligomers and subsequent polymerization in the crystals. This result provided a new environmentally benign procedure for the preparation of aromatic polyimide particles.

  16. Articles

    1. Thermal response of a PVCL–HA conjugate

      Jukka Niskanen, Mikko Karesoja, Vladimir Aseyev, Xing-Ping Qiu, Françoise M. Winnik and Heikki Tenhu

      Article first published online: 11 AUG 2015 | DOI: 10.1002/pola.27794

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      Diblock copolymers consisting of hyaluronic acid, HA, and poly(N-vinylcaprolactam), PVCL, have been synthesized. The blocks were first end functionalized and then coupled with click chemistry. The HA block consisted of 16–18 saccharide units and the PVCL block of ∼25 repeating units. HA-PVCL conjugate self-assembles in water upon heating into monodisperse, colloidally stable, hollow spherical particles whose size may be tuned with the heating rate of the solution.

    2. Synthesis of poly(arylene ether ketone)s bearing skeletal crown ether units for cation exchange membranes

      Bram Zoetebier, Sinem Tas, G. Julius Vancso, Kitty Nijmeijer and Mark A. Hempenius

      Article first published online: 9 AUG 2015 | DOI: 10.1002/pola.27752

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      Crown ether incorporation into the main chain of poly(arylene ether ketone)s turns these polymers into attractive membrane materials because of their potential ion selectivity. Hydroxy-functionalized dibenzo-18-crown-6 is used as monomer in step growth polymerization to form crown ether-bearing poly(arylene ether ketone)s. Membranes fabricated from sulfonated crown ether-bearing poly(arylene ether ketone)s show a lower potassium ion transport because of crown ether–cation interactions.

    3. Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

      Christian W. Pester, Justin E. Poelma, Benjaporn Narupai, Shrayesh N. Patel, Gregory M. Su, Thomas E. Mates, Yingdong Luo, Christopher K. Ober, Craig J. Hawker and Edward J. Kramer

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27748

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      Visible light-mediated radical polymerization allows for the fabrication of patterned diblock copolymer brushes. Surface properties of these model hydrophilic/hydrophobic ambiguous diblock brushes composed of anti-fouling relevant monomers were thoroughly characterized, and spatial patterning gives topographically and chemically well-defined surfaces. This strategy combines hydrophilic and hydrophobic properties on the micron length scale. Additionally, advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization were combined to achieve both high spatial definition and monomer tolerance.

    4. End group polarity and block symmetry effects on cloud point and hydrodynamic diameter of thermoresponsive block copolymers

      Xu Xiang, Xiaochu Ding, Ning Chen, Beilu Zhang and Patricia A. Heiden

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27757

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      Thermoresponse properties of linear and star block copolymers with 50% hydrophilic oligoethyleneacrylate and 50% more hydrophobic diethyleneglycolmethacrylate were studied for effects of different amphiphilic end groups. The cloud point and temperature range for the coil collapse of linear diblock copolymers were typically more sensitive to the effects of matching polar end groups to the more polar block than the linear triblock or star diblock copolymers. The effects of changing a polar chain end for a more polar chain end were significantly less than the effects of pairing the more polar end group with the more polar block.

    5. Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light

      Pu Xiao, Frédéric Dumur, Jing Zhang, Bernadette Graff, Fabrice Morlet-Savary, Jean Pierre Fouassier, Didier Gigmes and Jacques Lalevée

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27763

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      Naphthalic anhydride derivatives are promising photoinitiators for both the cationic polymerization and the free radical polymerization under blue light or polychromatic visible light. And the substituents in the naphthalic anhydride skeleton significantly affect their relative photoinitiation ability.

    6. Amphiphilic silica/fluoropolymer nanoparticles: Synthesis, tem-responsive and surface properties as protein-resistance coatings

      Hongpu Huang, Jia Qu and Ling He

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27785

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      Amphiphilic nanoparticles of SiO2-g-P(PEGMA)-b-P(12FMA) (150–170 nm) are prepared by SI-ATRP. The introduction of P(12FMA) segments not only provide prepared nanoparticles with obvious lower LCST and higher thermostability, but also obviously reduce the protein-repelling adsorption of films. Therefore, it is suggested to be used as protein-resistance coatings.

    7. Synthesis of water-soluble zwitterionic polysiloxanes

      Matthew Skinner, Ryan Selhorst and Todd Emrick

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27773

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      The facile preparation of water-soluble polysiloxanes containing pendent phosphorylcholine and sulfobetaine zwitterions is demonstrated. Zwitterionic polysiloxanes, synthesized by thiol-ene ‘click’ functionalization of vinyl-substituted siloxane polymers with zwitterionic thiols, were isolated with relatively high molecular weight and narrow molecular weight distribution. The surfactant characteristics and self-assembly behavior of these novel polymer amphiphiles in water are presented.

    8. Hyperbranched block copolymer from AB2 macromonomer: Synthesis and its reaction-induced microphase separation in epoxy thermosets

      Jingang Li, Yixin Xiang and Sixun Zheng

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27784

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      The synthesis of a hyperbranched block copolymer composed of poly(ε-caprolactone) (PCL) and polystyrene (PS) subchains via a copper-catalyzed Huisgen 1,3-dipolar cycloaddition polymerization is reported.

    9. Catalytic [2 + 2 + 2] cycloaddition polymerization of diyne–nitrile monomers in the presence of CoCl2-6H2O/diphosphine/Zn

      Yu-ki Sugiyama and Sentaro Okamoto

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27780

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      A cobalt-catalyzed [2 + 2 + 2] cocycloaddition reaction of 1,6-diynes and nitriles, providing substituted pyridines, has been applied to polymerization of diyne–nitrile monomers, the reaction of which proceeded smoothly in a step-growth fashion to provide linear polymers comprised with pyridine structure in a main chain.

    10. Copolymerization of isoprene with ethylene catalyzed by cationic half-sandwich fluorenyl scandium catalysts

      Gaixia Du, Jiaping Xue, Deqian Peng, Chao Yu, Hanghang Wang, Yuening Zhou, Jiaojiao Bi, Shaowen Zhang, Yuping Dong and Xiaofang Li

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27769

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      The cationic half-sandwich fluorenyl scandium species served as highly efficient and selective catalysts in isoprene polymerization and copolymerization with ethylene, affording cis−1,4-rich polyisoprenes and random or almost alternating isoprene-ethylene copolymers which are unavailable by the traditional catalysts. Besides, the isoprene incorporation and distribution in the copolymer chains can be controlled by changing the substituents of the fluorenyl ligand, thus generating different copolymers including 3,4-IP-alt-E and cis−1,4-IP-alt-E sequences.

    11. High solids TEMPO-mediated radical semibatch emulsion polymerization of styrene

      Roberto González-Blanco, Michael F. Cunningham and Enrique Saldívar-Guerra

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27771

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      A robust semicontinuous emulsion process for the nitroxide-mediated styrene polymerization is presented, using a bicomponent initiation system with TEMPO and potassium persulfate. Stable polystyrene latexes with solids contents of 5 to 40 wt %, high conversion (>95%), well controlled polymers (molecular weight dispersities lower than 1.4-1.5) and nitroxide efficiencies of nearly 100% are obtained, which constitutes a significant advance over prior efforts in TEMPO-mediated polymerization in aqueous dispersions.

  17. ArticleS

    1. Synthesis of high-order multiblock core cross-linked star polymers

      Thomas G. McKenzie, Jing M. Ren, Dave E. Dunstan, Edgar H. H. Wong and Greg G. Qiao

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27775

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      Core cross-linked star polymer nanoparticles with arms composed of sequence-defined multiblock copolymer structures have been synthesized for the first time via a one-pot copper-mediated controlled radical polymerization. The nature of the “arm-first” approach ensures that only linear macroinitiators with the desired block sequence are carried through to the final star structure. This technique represents a promising approach toward spatially resolved, sequence-defined polymeric nanoparticles.

  18. Articles

    1. Synthesis and characterization of polymer electrolytes based on cross-linked phenoxy-containing polyphosphazenes

      Chih-Hao Tsao, Mitsuru Ueda and Ping-Lin Kuo

      Article first published online: 6 AUG 2015 | DOI: 10.1002/pola.27781

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      A series of polymer electrolytes are prepared by reacting poly(phosphazene)s having 2-(2-methoxyethoxy)ethoxy and 2-(phenoxy)ethoxy units with 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (CYMEL) as a cross-linking agent. It is simple and reliable for controlling the cross-linking extent, thereby providing a straightforward way to produce a flexible polymer electrolyte membrane and useful model polymers to study the relationship between the cross-linking extents. The polymer electrolyte exhibits a maximum ionic conductivity of 5.36 × 10−5 S cm−1 at 100 °C.

    2. Effect of side chain conjugation lengths on photovoltaic performance of two-dimensional conjugated copolymers that contain diketopyrrolopyrrole and thiophene with side chains

      You-Ren Liu, Li-Hsin Chan and Horng-Yi Tang

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27767

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      Two new 2D conjugated copolymers, called PDPPMTD and PDPPBTD, were designed and synthesized for use in PSCs. The findings herein suggest that the subtle tuning of the chemical structure of the side chains appeared significantly to influence the Jsc and FF.

    3. Azide-functionalized nanoparticles as quantized building block for the design of soft–soft fluorescent polystyrene core—PAMAM shell nanostructures

      Krystyna Baczko, Hélène Fensterbank, Bruno Berini, Nadège Bordage, Gilles Clavier, Rachel Méallet-Renault, Chantal Larpent and Emmanuel Allard

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27772

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      This work reports the covalent association of azido-coated nanoparticles, amino-terminated PAMAM dendrons, and a Bodipy derivative that leads to well-defined fluorescent dendrimer-based nanostructures in the 20–30 diameter range. These nano-objects display absorption and emission maxima above 500 nm with brightness the same order of magnitude as Qdots.

    4. Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene

      Valeria Alzari, Daniele Nuvoli, Davide Sanna, Andrea Ruiu and Alberto Mariani

      Article first published online: 3 AUG 2015 | DOI: 10.1002/pola.27776

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      Frontal ring opening metathesis polymerization was successfully applied to the synthesis of copolymers of dicyclopentadiene and limonene. The presence of limonene was found to be crucial for many polymerization parameters and confers new and particular characteristics to polymer materials.

    5. A facile synthesis of catechol-functionalized poly(ethylene oxide) block and random copolymers

      Kaila M. Mattson, Allegra A. Latimer, Alaina J. McGrath, Nathaniel A. Lynd, Pontus Lundberg, Zachary M. Hudson and Craig J. Hawker

      Article first published online: 31 JUL 2015 | DOI: 10.1002/pola.27749

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      A modular strategy, starting from readily available methyl eugenol, to imbed protected catecholic moieties at controlled levels within polyethers is presented. This simple, high-yielding synthesis represents the first time catechols have been controllably dispersed throughout polyethylene oxide (PEO)-based polymer backbones. The precise tunability afforded by this system can enable systematic investigation of the effects that variables such as molecular weight, catechol incorporation, and catechol location can have on surface-anchored PEO.

    6. Photochemical stability of dicyano-substituted poly(phenylenevinylenes) with different side chains

      Logan P. Sanow, Jianyuan Sun and Cheng Zhang

      Article first published online: 31 JUL 2015 | DOI: 10.1002/pola.27755

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      The photodegradation mechanism study has been conducted on poly(2,5-dioctyl-1,4-phenylene-1,2-dicyanovinylene) (C8-diCN-PPV) and poly[2,5-bis(decyloxy)−1,4-phenylene-1,2-dicyanovinylene] (RO-diCN-PPV) to understand the reason behind the faster photodegradation of C8-diCN-PPV which has a lower LUMO. In both polymers, radical superoxide anion mechanism, which is responsible for electron-rich RO-PPVs, is found to be energetically unfavorable due to diCN substitution. Combined IR, UV–vis, photoluminescence, and phosphorescence spectroscopies study indicates that singlet oxygen is the main culprit for photodegradation of both polymers.

    7. A visible light responsive azobenzene-functionalized polymer: Synthesis, self-assembly, and photoresponsive properties

      Guojie Wang, Dong Yuan, Tingting Yuan, Jie Dong, Ning Feng and Guoxiang Han

      Article first published online: 29 JUL 2015 | DOI: 10.1002/pola.27747

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      An amphiphilic tetra-o-methoxy-substituted-azobenzene-functionalized poly(acrylic acid) was synthesized via the postpolymerization modification method, which can exhibit the trans-to-cis photoswitching under green light irradiation at 520 nm and the cis-to-trans photoswitching under blue light irradiation at 420 nm in both solution and aggregate state. The fluorescence of loaded Nile Red in the self-assembled polymer nanoparticles can be tuned upon the visible light irradiation.

    8. Graft modification of crystalline nanocellulose by Cu(0)-mediated SET living radical polymerization

      Hai-Dong Wang, Ryan D. Roeder, Ralph A. Whitney, Pascale Champagne and Michael F. Cunningham

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27754

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      Cu(0)-catalyzed SET living radical polymerization was used to graft poly(methyl acrylate) from a crystalline nanocellulose (CNC) surface. The polymer grafting step process exhibits fast polymerization kinetics and a very low level of copper consumption. The resulting polymerization medium is clear with almost no color, indicating low dissolved copper concentrations.

    9. Free radical polymerization of caffeine-containing methacrylate monomers

      Ashley M. Nelson, Sean T. Hemp, Jessica Chau and Timothy E. Long

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27756

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      A two-step synthesis involving a UV-induced photoreaction transformed the renewable resource caffeine into a polymerizable methacrylate. Free radical polymerization with 2-ethylhexyl methacrylate afforded novel copolymers containing covalently bound pendant caffeine. 1H NMR and UV-vis absorbance spectroscopy confirmed caffeine incorporation and SEC elucidated high molecular weight copolymers resulted. Caffeine increased both the glass transition temperature and modulus of the copolymers at low mol % incorporation revealing the potential for caffeine as a comonomer in thermoplastic elastomers.

    10. Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization

      Veronika Strehmel and Volker Senkowski

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27760

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      Group transfer polymerization of ionic liquid methacrylates bearing the same anion as the hydrophobic ionic liquid used as solvent occurs more efficient compared to traditional methacrylates. The hydrophobic ionic liquid solvent influences group transfer polymerization of both traditional and ionic liquid methacrylates. The anion of the ionic liquid derives from a super acid. The ionic liquid additionally shows catalytic activity.

    11. Fabric-hydrogel composite membranes for culturing microalgae in semipermeable membrane-based photobioreactors

      Seung-Yong Lee, Z-Hun Kim, Hwa Yeon Oh, Younghoon Choi, Hanwool Park, Daewoo Jung, Jong-Min Kim, Yang Ho Na, Sang-Min Lim, Choul-Gyun Lee and Jin-Kyun Lee

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27770

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      Fabric-hydrogel composite membranes (FHCMs) are proposed as semipermeable materials for the construction of photobioreactors. A cotton fabric inside the hydrogel matrix endows the composite with tensile strength, which enables casting of FHCMs into thin membranes. In permeability coefficient measurements of inline image ions, it reached as high as 1.2 × 10−8 m2 min−1. In microalgal culture, a photobioreactor with a FHCM could maintain sufficient inline image ion concentration and pH of the culture broth, supporting microalgal growth.

    12. High refractive index materials: A structural property comparison of sulfide- and sulfoxide-containing polyamides

      Ali Javadi, Ebrahim Abouzari-Lotf, Shahram Mehdipour-Ataei, Masoumeh Zakeri, Mohamed Mahmoud Nasef, Arshad Ahmad and Adnan Ripin

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27764

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      Highly refractive polyamides bearing chlorine, sulfide, or sulfoxide linkages and ortho-linked patterned substitution are synthesized. Beside high solubility and thermal stability, the polymers exhibited desired optical properties including high optical transparency, high refractive indices, and low birefringence.

    13. PEGDA-based luminescent polymers prepared by frontal polymerization

      Javier Illescas, Yessica S. Ramírez-Fuentes, Gerardo Zaragoza-Galán, Pasquale Porcu, Alberto Mariani and Ernesto Rivera

      Article first published online: 28 JUL 2015 | DOI: 10.1002/pola.27768

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      Novel copolymers of PEGDA and 1-pyrenebutyl acrylate (PyBuAc), used as a fluorescent probe, were synthesized by radical polymerization. Besides, the optical properties of these materials were studied by absorption and fluorescence spectroscopy. The obtained copolymers exhibited a broad absorption band, and from the fluorescence spectra, no excimer emission was observed. It was possible to tune the color of the emitted light with the variation of the pyrene content in the samples.

    14. Synthesis and evaluation of new phosphonic acid-functionalized acrylamides with potential biomedical applications

      H. Betul Bingol, Ayse Altin, Tugba Bal, Sesil Agopcan-Cinar, Seda Kizilel and Duygu Avci

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27746

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      Three acrylamides containing phosphonic acid groups were synthesized and evaluated to investigate the relationship between monomer structure and polymerization reactivity/adhesion properties. They were found to be suitable for use as self-etching adhesive monomers because of their etching ability, hydrolytic stability, and copolymerizability with dental monomers. Furthermore, these monomers were used in the fabrication, characterization, and mineralization of hydrogels for tissue engineering applications.

    15. Light-induced controlled free radical polymerization of methacrylates using iron-based photocatalyst in visible light

      Ankushi Bansal, Pawan Kumar, Chandra D. Sharma, Siddharth S. Ray and Suman L. Jain

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27744

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      An efficient, inexpensive and less toxic iron-based photocatalyst is developed [i.e., Fe(bpy)3(PF6)2] for light-initiated controlled polymerization of methacrylates using α-bromoisobutyrate (EBriB) as an initiator under visible light.

    16. Biomimetic triblock and multiblock copolymers containing l-Phenylalanine moieties showing healing and enhanced mechanical properties

      Michael Hendrich, Lars Lewerdomski and Philipp Vana

      Article first published online: 27 JUL 2015 | DOI: 10.1002/pola.27753

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      Biomimetic triblock and multiblock copolymers of methyl acrylate and N-acryloyl-l-phenylalanine were synthesized via RAFT polymerization mimicking the structure of spider dragline silk. Tensile testing shows that the hydrogen bonding monomer induces a pronounced toughness increase. The new copolymers display a very strong healing effect, with the toughness being increased after drawing, breaking, and healing. Already, a very small content of only 0.1 mol % of N-acryloyl-l-phenylalanine improves the mechanical properties of these polymers significantly.

    17. Reactive copolymer functionalized graphene sheet for enhanced mechanical and thermal properties of epoxy composites

      Qiang Ma, Jing Luo, Yuanxun Chen, Wei Wei, Ren Liu and Xiaoya Liu

      Article first published online: 24 JUL 2015 | DOI: 10.1002/pola.27751

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      A novel reactive copolymer VCz–GMA containing carbazole and epoxide group was designed, synthesized and employed to noncovalently functionalize graphene sheet (GNS) for preparing epoxy nanocomposites with enhanced mechanical properties. VCz–GMA facilitates the exfoliation/dispersion level of GNs in epoxy matrix and serves as a linker between GNS and epoxy with improved compatibility and interfacial interaction. The obtained composite showed a remarkable enhancement in both mechanical and thermal property than either the pure epoxy or the GNS/epoxy composites.

    18. Nanopatterning and micropatterning of cobalt containing block copolymers via phase-separation and lithographic techniques

      Mahboubeh Hadadpour and Paul J. Ragogna

      Article first published online: 17 JUL 2015 | DOI: 10.1002/pola.27745

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      Solution self-assembly of a BCP consisting of cobalt containing metallopolymer block and a PDMS block resulted in spherical micelles with metallic core and PDMS corona. Solid-state self-assembly produces hexagonal domains of metallopolymer in a PDMS matrix. Magnetic ceramic is produced by pyrolysis of the bulk self-assembled BCP. This material is used as ink in pattern transfer via the μCP lithography method.

    19. Versatile and controlled functionalization of polyferrocenylsilane-b-polyvinylsiloxane block copolymers using a N-hydroxysuccinimidyl ester strategy

      Charlotte E. Boott, David J. Lunn and Ian Manners

      Article first published online: 14 JUL 2015 | DOI: 10.1002/pola.27727

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      This article reports the introduction of a N-hydroxysuccinimidyl ester group onto the pendant vinyl group of poly(ferrocenyldimethyl)silane-b-polyvinylsiloxane copolymers which provides a route to incorporate a range of functionalities previously inaccessible using other methods.

    20. Low-potential facile electrosynthesis of free-standing poly(1H-benzo[g]indole) film as a yellow-light-emitter

      Ling Wang, Dan Zhao, Changlong Liu and Guangming Nie

      Article first published online: 7 JUL 2015 | DOI: 10.1002/pola.27738

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      Free-standing poly(1H-benzo[g]indole) films are synthesized electrochemically in boron trifluoride diethyl etherate at low potentials. Poly(1H-benzo[g]indole) with low band gap value (1.59 eV) shows good electrochemical behavior and better thermal stability. Fluorescent spectral studies indicate that solid-state Poly(1H-benzo[g]indole) film is a good yellow-light-emitter.

    21. Cyclopentyl methyl ether: A new green co-solvent for supplemental activator and reducing agent atom transfer radical polymerization

      Pedro Maximiano, Joana P. Mendes, Patrícia V. Mendonça, Carlos M. R. Abreu, Tamaz Guliashvili, Arménio C. Serra and Jorge F. J. Coelho

      Article first published online: 4 JUL 2015 | DOI: 10.1002/pola.27736

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      A new green solvent, cyclopentyl methyl ether, is used for the first time in solvent mixtures for the successful supplemental activator and reducing agent atom transfer radical polymerization of both activated and non-activated monomers. The “green” nature of the solvent along with the use of low concentrations of soluble metal catalyst during the polymerization makes this technique very attractive for the preparation of polymers for biomedical applications.

    22. RAFT made methacrylate copolymers for reversible pH-responsive nanoparticles

      Turgay Yildirim, Alexandra C. Rinkenauer, Christine Weber, Anja Traeger, Stephanie Schubert and Ulrich S. Schubert

      Article first published online: 2 JUL 2015 | DOI: 10.1002/pola.27734

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      A library of well-defined copolymers of methyl methacrylate (MMA) with 2-(dimethylamino) ethyl methacrylate (DMAEMA), 2-(tert-butylamino)ethylmethacrylate (tBAEMA) and 2-aminoethyl methacrylate hydrochloride (AEMA HCI) was synthesized via RAFT polymerization. The controlled nature of the radical polymerization was demonstrated by kinetic studies. Well-defined nanoparticles from the synthesized copolymers with varying sizes were successfully prepared via the nanoprecipitation method. Depending on the structure and amount of the amino content, the obtained nanoparticles reveal a reversible pH-response. The nanoparticles did not exhibit any cytotoxic effect on L929 cells.


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