Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 21

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

Impact Factor: 3.543

ISI Journal Citation Reports © Ranking: 2012: 12/83 (Polymer Science)

Online ISSN: 1099-0518

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


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  1. Articles

    1. Polyimide polydimethylsiloxane triblock copolymers for thin film composite gas separation membranes

      Paul A. Gurr, Joel M. P. Scofield, Jinguk Kim, Qiang Fu, Sandra E. Kentish and Greg G. Qiao

      Article first published online: 30 SEP 2014 | DOI: 10.1002/pola.27401

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      A series of novel triblock copolymers consisting of difunctional hard polyimide coupled to soft polydimethylsiloxane is prepared by a combination of condensation polymerization, in situ functionalization, and click coupling. The polymers are demonstrated to successfully coat onto the surface of a crosslinked polydimethylsiloxane substrate forming a highly permeable selective thin film composite membrane for CO2 gas separation.

  2. Erratum

    1. You have free access to this content
      Erratum: Evaluation Of proton conductivity of sulfonated polyimide/dihydroxy naphthalene charge-transfer complex hybrid membranes

      Liana Christiani, Sandra Hilaire, Kazunari Sasaki and Masamichi Nishihara

      Article first published online: 30 SEP 2014 | DOI: 10.1002/pola.27419

      This article corrects:
  3. Articles

    1. Enhancing electrochromic contrast and redox stability of nanostructure polypyrrole film doped by heparin as polyanion in different solvents

      Naader Alizadeh and Farnaz Tavoli

      Article first published online: 29 SEP 2014 | DOI: 10.1002/pola.27398

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      The spectroelectrochemical studies in different solvents show that the electrochromic properties of polymer film such as optical contrast, switching time, film stability, and coloration efficiency are greatly enhanced due to the incorporation of Hep.

    2. Patterned growth of oriented 2D covalent organic framework thin films on single-layer graphene

      John W. Colson, Jason A. Mann, Catherine R. DeBlase and William R. Dichtel

      Article first published online: 29 SEP 2014 | DOI: 10.1002/pola.27399

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      Covalent organic frameworks (COFs) are crystalline network polymers that feature permanent porosity, high surface areas, and predictable organization of their monomers. COFs are typically isolated as insoluble powders, but high-quality thin films are needed to fully explore their potential applications. This manuscript demonstrates that suitable solvent mixtures promote COF growth selectively on single-layer graphene. Lithography of the graphene provides patterned COF films, offering unprecedented control of COF growth relevant to their incorporation into device architectures.

    3. Polymerization of an epoxy-containing silacyclobutane and its application to networked polymer synthesis

      Kozo Matsumoto, Yoshinori Goto, Naoki Nagao and Takeshi Endo

      Article first published online: 29 SEP 2014 | DOI: 10.1002/pola.27407

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      A silacyclobutane having an epoxy group (OBMSB) and 1,1-diethylsilacyclobutane (DESB) were copolymerized to obtain polycarbosilane having epoxy pendant groups. These polymers were crosslinked by the following ring-opening polymerization of epoxy moieties with cationic initiators to provide flexible networked polycarbosilanes.

    4. Synthesis of unsaturation containing P(VDF-co-TrFE-co-CTFE) from P(VDF-co-CTFE) in one-pot catalyzed with Cu(0)-based single electron transfer living radical polymerization system

      Xin Hu, Shaobo Tan, Guoxin Gao, Yunchuan Xie, Qinzhuo Wang, Na Li and Zhicheng Zhang

      Article first published online: 26 SEP 2014 | DOI: 10.1002/pola.27410

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      Cu(0)-catalyzed One-Pot strategy with well-controlled and environmental friendly characters was successfully developed to synthesize unsaturation containing P(VDF-co-TrFE-co-CTFE), which combine the concurrent single electron transfer chain transfer reaction (SET-CTR) and the dehydrochlorination reaction of commercial P(VDF-co-CTFE).

    5. Synthesis of AB3-type miktoarm star polymers with steroid core via a combination of “Click” chemistry and ring opening polymerization techniques

      Erdinc Doganci, Mesut Gorur, Cavit Uyanik and Faruk Yilmaz

      Article first published online: 26 SEP 2014 | DOI: 10.1002/pola.27406

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      Novel AB3-type miktoarm and A4 star polymers with steroid core were synthesized via a combination of “click” chemistry and ring opening polymerization (ROP) methods. The chemical structures of the obtained star polymers were investigated via FT-IR and 1H NMR spectroscopic techniques. Their thermal properties were investigated thoroughly using DSC and TGA experiments.

    6. Synthesis and characteristics of poly(methyl methacrylate-co-methacrylic acid)/poly(methacrylic acid-co-N-isopropylacrylamide) thermosensitive semi-hollow latex particles and their application to drug carriers

      Chia-Fen Lee, Mei-Ling Hsu, Chun-Hsun Chu and Tsung-Yuan Wu

      Article first published online: 26 SEP 2014 | DOI: 10.1002/pola.27411

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      Part of the poly(methyl methacrylate-co-methacrylic acid) (poly(MMA-MAA)) linear core of linear poly(MMA-MAA)/crosslinking poly(methacrylic acid-co-N-isopropylacrylamide) (poly(MAA-NIPAAm)) core–shell solid latex particles was dissolved by ammonia to form the poly(MMA-MAA)/poly(MAA-NIPAAm) thermosensitive semi-hollow latex particles. The latex particles with the shell composition of crosslinking agent 5% failed to form the semi-hollow structure. Both of the latex particles with the shell composition of crosslinking agent 3% and 1% formed the semi-hollow structure successfully.

    7. Aggregation of polythiophene homopolymer and block copolymer in solution utilizing the characteristics of pyridine at the side chain

      Koji Takagi, Eiki Kawagita, Ryo Kouchi and Junpei Kawai

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27403

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      The synthesis and aggregation of polythiophene homopolymer and block copolymer bearing pyridine at the side chain were investigated in solution. A block copolymer was found to form nanometer-scale aggregates in selective solvent, which was characterizaed by UV-vis, fluorescence, NMR, and DLS measurements.

    8. Insights into propylene/ω-halo-α-alkenes copolymerization promoted by rac-Et(Ind)2ZrCl2 and (pyridyl-amido)hafnium catalysts

      Xiao-Yan Wang, Ying-Yun Long, Yong-Xia Wang and Yue-Sheng Li

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27409

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      Differences between rac-Et(Ind)2ZrCl2 and dimethyl (pyridyl-amido)hafnium in catalyzing the propylene/ω-halo-α-alkene copolymerization were studied under similar conditions. Contrasting the two catalysts, including the distinct catalytic performances and the discrepant characteristics of the copolymers afforded by them, holds importance for the development of halogen-resistant catalysts and the preparation of functional polyolefins.

    9. A glucose sensor via stable immobilization of the GOx enzyme on an organic transistor using a polymer brush

      M. Elizabeth Welch, Thomas Doublet, Christophe Bernard, George G. Malliaras and Christopher K. Ober

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27392

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      A PEDOT:PSS based microelectrode, which measures neuronal activities in vivo, is enhanced through the incorporation of polymer brushes. This biosensor requires the tethering of glucose oxidase for specific charge exchange reactions to occur between the biological media and the conducting polymer sensor. Polymer brushes are used to anchor these molecules to the electrode surface without altering the conductivity of the transistor.

    10. Supramolecular inclusion complexes of a star polymer containing cholesterol end-capped poly(ε-caprolactone) arms with β-cyclodextrin

      Erdinc Doganci, Mesut Gorur, Cavit Uyanik and Faruk Yilmaz

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27408

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      A new star polymer possessing cholesterol end-capped poly(ε-caprolactone) arms were prepared. The effects of the cholesterol end-groups on the stability of the inclusion complexes of the star polymer with β-cyclodextrin were thoroughly investigated.

  4. Rapid Communications

    1. A facile surface treatment utilizing binary mixtures of ammonium salts and polar solvents for multiply enhancing thermoelectric PEDOT: PSS films

      Tsung-Che Tsai, Tsung-Han Chen, Hsiu-Cheng Chang, Chun-Hua Chen, Yi-Chia Huang and Wha-Tzong Whang

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27402

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      An innovative composite recipe coupling binary mixtures of ammonium salts of Ammonium formate (AF) and polar solvents 2-methoxyethanol (ME) has been successfully demonstrated as an effective surface-treatment reagent for significantly improving the thermoelectric performance of the baked poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films. The unique combination opens a new avenue to simultaneously improve the Seebeck coefficient and electrical conductivity of the baked PEDOT:PSS films for obtaining the remarkably enhanced power factor of ∼20 μW/mK2 and the ZT of 0.033.

  5. Articles

    1. Biobased vinyl levulinate as styrene replacement for unsaturated polyester resins

      Sylvain Cousinet, Ali Ghadban, Imène Allaoua, Frédéric Lortie, Daniel Portinha, Eric Drockenmuller and Jean-Pierre Pascault

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27397

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      Vinyl levulinate (VL) is used as a biobased reactive diluent to develop styrene-free unsaturated polyester resins (UPRs). Defect-free, slightly yellow, transparent, and rigid thermosets are obtained after a mild curing cycle. Due to unfavorable reactivity ratios (rVL = 0.01 and rDEF = 0.81 at 60 °C in DMSO) about 5.5 wt % of unpolymerized VL remains inside the network and acts as a plasticizer. Consequently, VL-based UPRs have lower mechanical properties than standard St-based commercial UPRs.

    2. Biodegradable photocrosslinkable poly(depsipeptide-co-ε-caprolactone) for tissue engineering: Synthesis, characterization, and In vitro evaluation

      Laura Elomaa, Yunqing Kang, Jukka V. Seppälä and Yunzhi Yang

      Article first published online: 25 SEP 2014 | DOI: 10.1002/pola.27400

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      A novel photocrosslinkable poly(ester amide) based on ε-caprolactone and l-alanine-derived depsipeptide is synthesized, and the use of the copolymer in tissue engineering applications is demonstrated by fabricating three-dimensional (3D) scaffolds by stereolithography. The introduction of depsipeptides into photocrosslinkable polyesters increases the mechanical properties of the polymers and accelerates their degradation rate. The new photocrosslinkable poly(ester amide) synthesized in this study expands the repertoire of currently available biomaterials suitable for 3D printing of high-resolution tissue engineering scaffolds.

    3. Synthesis, physicochemical characterization, and self-assembly of linear, dibranched, and miktoarm semifluorinated triphilic polymers

      W. B. Tucker, A. M. McCoy, S. M. Fix, M. F. Stagg, M. M. Murphy and S. Mecozzi

      Article first published online: 23 SEP 2014 | DOI: 10.1002/pola.27394

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      Three classes of semifluorinated amphiphiles were synthesized and their aggregation behavior characterized. It was found that critical micelle concentration, microviscosity and aggregate stability were related to amphiphile architecture and the size of the fluorocarbon segment. Furthermore, it has been shown that a hydrophobic molecule—paclitaxel—can be encapsulated within the semifluorinated micelles derived from these polymers, thus demonstrating the potential to encapsulate hydrophobic species within a lipophilic shell without necessitating a lipophilic core.

    4. Synthesis and characterization of biodegradable amphiphilic ABC Y-shaped miktoarm terpolymer by click chemistry for drug delivery

      Yanfeng Chu, Huan Yu, Yunti Zhang, Guangyan Zhang, Yingying Ma, Renxi Zhuo and Xulin Jiang

      Article first published online: 23 SEP 2014 | DOI: 10.1002/pola.27396

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      Biodegradable amphiphilic ABC Y-shaped miktoarm star terpolymer for drug delivery was designed and synthesized by click reaction between monoazido-midfunctionalized mPEG-PCL and alkynyl-terminated polyaspartamide derivative. The obtained Y-shaped asymmetric heteroarm triblock copolymer self-assembled into micelles and loaded hydrophobic drug. The DOX-loaded micelles displayed obvious anticancer activity similar to free DOX, whereas blank polymeric micelles were nontoxic.

    5. Synthesis of poly(ester-amide) dendrimers based on 2,2-Bis(hydroxymethyl) propanoic acid and glycine

      David Pahovnik, Anja Čusak, Sebastjan Reven and Ema Žagar

      Article first published online: 19 SEP 2014 | DOI: 10.1002/pola.27391

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      An approach for preparation of poly(ester-amide) dendrimers with hydroxyl functional groups based on 2,2-bis(hydroxymethyl) propanoic acid (bis-MPA) and glycine is presented. The applicability of these dendrimers in comparison with commercially available dendritic polymers (bis-MPA dendrimers, Hybrane S1200 hyperbranched polymer) to improve the solubility of poorly water-soluble antidiabetic drug glimepiride by preparation of solid dispersions is investigated.

    6. One donor–two acceptor (D–A1)-(D–A2) random terpolymers containing perylene diimide, naphthalene diimide, and carbazole units

      Lisa M. Kozycz, Dong Gao, Andrew J. Tilley and Dwight S. Seferos

      Article first published online: 19 SEP 2014 | DOI: 10.1002/pola.27395

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      Five donor-acceptor copolymers containing various amounts of two acceptor units are synthesized by Suzuki coupling polymerization and the composition dependence of their optical and electronic properties is studied. The copolymers are tested as acceptor materials in all-polymer solar cells and the highest device efficiency is obtained for the PDI parent copolymer using PBDTTT-C as the donor material.

    7. Cu(I) camphor coordination polymers: Synthesis and study of the catalytic activity for cyclization of acid 4-pentyn-1-oic

      Tiago A. Fernandes, Adelino M. Galvão, Ana M. Botelho do Rego and M. Fernanda N. N. Carvalho

      Article first published online: 19 SEP 2014 | DOI: 10.1002/pola.27393

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      The synthesis and characterization, as well as the computational optimized structural arrangement, of Cu(I) coordination polymers with camphor-derived ligands (L) having CuCl to L ratios higher (3:1 or 4:1) than the former (2:1) are reported. The compounds were shown to be active catalysts for synthesis of lactones through cyclization acid 4-pentyn-1-oic, either in solution or under solvent-free conditions. A mechanism is proposed based on calculation of constants made by fitting the 1H NMR data.

    8. Novel poly(l-lactide)/poly(d-lactide)/poly(tetrahydrofuran) multiblock copolymers with a controlled architecture: Synthesis and characterization

      Lorenza Gardella, Dario Cavallo, Samuele Colonna, Alberto Fina and Orietta Monticelli

      Article first published online: 19 SEP 2014 | DOI: 10.1002/pola.27389

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      A two-stage synthetic route towards novel multiblock copolymers with a controlled architecture based on PDLA-PLLA-PTHF-PLLA-PDLA pentablock unit is developed. This approach affords materials combining the high rigidity and strength (other than improved thermal resistance) of the hard stereocomplex crystallites with the flexibility imparted by the soft block, whereby their properties can be finely tailored through the composition of the basic pentablock units without limitations on the final molecular weight.

  6. Highlights

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      Orthogonal multiple click reactions in synthetic polymer chemistry

      Umit Tunca

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27379

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      This review highlights the concept of multiple click reaction strategy which is utilized for design and synthesis of well-defined complex macromolecular structures as well as multifunctionalization of well-defined polymers. This review examines the click combinations mainly from double to quadruple and additionally from the most frequently used to the least.

  7. Articles

    1. Crosslinking-induced morphology change of latex nanoparticles: A study of RAFT-mediated polymerization in aqueous dispersed media using amphiphilic double-brush copolymers as reactive surfactants

      Yukun Li, Leela Christian-Tabak, Vivien Li Fong Fuan, Jiong Zou and Chong Cheng

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27387

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      Amphiphlic brush copolymers with each graft junction carrying one hydrophilic graft and one hydrophobic graft are synthesized and characterized. They are further used as both surfactants and polyfunctional RAFT agents for radical polymerization of styrene in miniemulsions. Depending on whether crosslinker is present in the polymerization systems, spherical and vesicular latex nanoparticles are obtained, respectively. The mechanism for such unusual crosslinking-induced morphology change of latex nanoparticles is discussed.

    2. Visible light-induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac-[Ir(ppy)]3

      Qian Liu, Lianying Liu, Yuhong Ma, Changwen Zhao and Wantai Yang

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27390

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      A new visible light-induced controlled radical polymerization of methacrylates, such as MMA, GMA, and TFEMA, with perfluoro-1-iodohexane (CF3(CF2)5I) as the initiator in the presence of a photoredox catalyst (fac-[Ir(ppy)3]) was developed. This method was used to successfully synthesize a clean diblock copolymer PMMA-b-PGMA with PMMA-I as the macroinitiator.

    3. Thermally curable organic/inorganic hybrid polymers as gate dielectrics for organic thin-film transistors

      Jong-Woon Ha, Yuntae Kim, Jeongkyun Roh, Fei Xu, Jong Il Park, Jeonghun Kwak, Changhee Lee and Do-Hoon Hwang

      Article first published online: 15 SEP 2014 | DOI: 10.1002/pola.27388

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      New low-temperature curable organic/inorganic hybrid polymers were designed and synthesized as gate dielectrics for organic thin-film transistors. The synthesized insulators as gate dielectric layers had higher hole mobilities (up to 0.36 cm2/Vs) than a device using thermally cross-linked poly(vinyl phenol) and melamine as the gate dielectric layer (0.18 cm2/Vs).

    4. Synthesis of novel cyclic olefin polymers with excellent transparency and high glass-transition temperature via gradient copolymerization of bulky cyclic olefin and cis-cyclooctene

      Ji-Xing Yang, Jing Cui, Ying-Yun Long, Yan-Guo Li and Yue-Sheng Li

      Article first published online: 13 SEP 2014 | DOI: 10.1002/pola.27386

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      Novel Cyclic Olefin Polymers (COPs) with high Tg (up to 201.2 °C) and excellent transparency (transmittance >88%) have been synthesized for the first time via gradient ring-opening metathesis copolymerization of bulky norbornene derivative (HBMN) with cis-cyclooctene (COE). To get amorphous copolymers with only one Tg, high HBMN/COE mole ratio and short polymerization time are preferred. In sharp contrast, all the films of HBMN/COE block copolymers are opaque and show decreased film forming ability.

    5. Columnar nanostructured polymer films containing ionic liquids in supramolecular one-dimensional nanochannels

      Akihiro Yamashita, Masafumi Yoshio, Seiya Shimizu, Takahiro Ichikawa, Hiroyuki Ohno and Takashi Kato

      Article first published online: 12 SEP 2014 | DOI: 10.1002/pola.27380

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      Supramolecular self-assembly of a diol-functionalized wedge-shaped molecule having polymerizable groups and an imidazolium-based ionic liquid leads to the induction of columnar liquid-crystalline phases. In situ photopolymerization of the columnar assemblies aligned by the application of shearing force provides a new type of columnar nanostructured polymer films with one-dimensionally ordered ionic liquids. Anisotropic ion conduction is achieved for the polymer films.

    6. Well-defined PE-b-PDMS diblock copolymers via the combination of thiol-ene click and esterification reactions: Facile synthesis and compatibilization for HDPE/silicone oil blends

      Zhixian Xu, Suyun Jie and Bo-Geng Li

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27381

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      Well-defined PE-b-PDMS diblock copolymers have been synthesized by the combination of radical initiated thiol-ene click and subsequent esterification reactions, which are proved to be an effective compatibilizer with low loading concentration in HDPE/silicone oil blends.

    7. Preparation and characterization of narrow compositional distribution polyampholytes as potential biomaterials: Copolymers of N-(3-Aminopropyl)methacrylamide hydrochloride (APM) and methacrylic acid (MAA)

      Ankita Dubey, Nicholas A. D. Burke and Harald D. H. Stöver

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27377

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      Adjusting the methacrylic acid (MAA) to sodium methacrylate (NaMAA) ratio, in copolymerizations with a cationic monomer N-(3-aminopropyl)methacrylamide hydrochloride (APM), can lead to effective APM/MAA reactivity ratios of unity. This results in copolymerizations without the otherwise common compositional drift, and produces well-defined APM/MAA copolymers with solubilities responsive to composition, pH, temperature, and salt that are of interest as building blocks for biomaterials.

  8. Rapid Communication

    1. A turn-off fluorescent substrate for horseradish peroxidase improves the sensitivity of ELISAs

      Abhinav P. Acharya, Payel Sen, Kiana Aran, Austin B. Gardner, Mohammad Rafi, Deborah Dean and Niren Murthy

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27376

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      A new turn-off fluorescent substrate for horseradish peroxidase is introduced, termed clics, which enhance the sensitivity of commercial enzyme-linked immunosorbant assays (ELISA) by 32-fold and detect chlamydial infections in patients. Clics are cost-effective, stable, and can be easily incorporated in commercial ELISA kits, and therefore should have a great impact in the fields of medicine and biology.

  9. Articles

    1. Synthesis and photovoltaic properties of conjugated D–A copolymers based on thienyl substituted pyrene and diketopyrrolopyrrole for polymer solar cells

      Ning Wang, Xichang Bao, Yan Yan, Dan Ouyang, Mingliang Sun, V. A. L. Roy, Chun Sing Lee and Renqiang Yang

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27378

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      A new donor-acceptor (D-A) conjugated copolymer (PDTPyDPP), comprising thienyl substituted pyrene as D building block and diketopyrrolopyrrole (DPP) as A unit, was synthesized and showed good light-harvesting characteristic.

    2. Poly(oxanorbornenedicarboximide)s dendronized with amphiphilic poly(alkyl ether) dendrons

      Xiaoli Liang, Mani K. Sen, Jo-Ann Jee, Oleg Gelman, Jeannette E. Marine, Kenneth Kan, Maya K. Endoh, Deborah A. Barkley, Tadanori Koga and Jonathan G. Rudick

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27385

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      A new family of dendrons, amphiphilic poly(alkyl ether) dendrons, are readily polymerized in a living manner. Ring-opening metathesis polymerization of the dendritic macromonomers yields single polymer molecules and cylindrical core-shell nanostructures with narrow molecular weight distribution and a controlled degree of polymerization.

    3. Different synthetic pathways of nanoparticle-cored dendrimers (NCDs): Effects on the properties and their application as redox active centers

      Julieta I. Paez, Pablo Froimowicz, Katharina Landfester, Verónica Brunetti and Miriam Strumia

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27375

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      Nanoparticle-cored dendrimers (NCDs) with diverse chemical and structural features are synthesized via surface functionalization of iron oxide nanoparticles and by combining a silane coupling agent and dendritic moieties. The nanostructure of the material is controlled not only by the information programmed into the dendritic branches, but also by the presence of other organic molecules within the modifying layer, by the molecular ordering, and by the interaction between the different modifiers and with the dispersing media, affecting macroscopic and physicochemical properties.

    4. Norbornene/n-Butyl methacrylate copolymerization over α-Diimine nickel and palladium catalysts supported on multiwalled carbon nanotubes

      Ping Huo, Wanyun Liu, Xiaohui He and Yiwang Chen

      Article first published online: 8 SEP 2014 | DOI: 10.1002/pola.27384

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      The covalently immobilized multiwalled carbon nanotubes (MWNTs) supported three-dimensional geometry α-diimine nickel, palladium catalysts exhibit high activities and productivities in norbornene homopolymerization or copolymerization with polar monomer. MWNTs are dispersed uniformly in polymers and wrapped by polymers to squeeze out of spherical particles, leading to the enhanced processability and mechanical properties.

    5. Photoresponsive polymers and block copolymers by molecular recognition based on multiple hydrogen bonds

      Alberto Concellón, Eva Blasco, Milagros Piñol, Luis Oriol, Isabel Díez, Cristina Berges, Carlos Sánchez-Somolinos and Rafael Alcalá

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27373

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      The preparation of a series of photoaddressable supramolecular materials is demonstrated by mixing different polymers, which contain 2,6-diacylaminopyridine derivative units, and azobenzene chromophores having thymine (tAZO) or carboxylic groups with a dendritic structure (dAZO), which can form either three or two hydrogen bonds with the 2,6-diacylaminopyridine groups, respectively. Homogeneous materials are obtained with full complexation degrees without showing macrophase separation. We have also studied thermal, optical and assembly properties of these supramolecular materials.

    6. Stabilization and functionalization of single-walled carbon nanotubes with polyvinylpyrrolidone copolymers for applications in aqueous media

      Brian V. Popp, Dillon H. Miles, Jake A. Smith, Irene M. Fong, Matteo Pasquali and Zachary T. Ball

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27365

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      Polyvinylpyrrolidone copolymers permit the synthesis of carbon nanotubes that are stable to significant pH gradients, allowing noncovalent functionalization with dye molecules and control over surface charge.

  10. Rapid Communications

    1. Polarity reversal of nanoparticle surfaces by the use of light-sensitive polymeric emulsifiers

      Robert Dorresteijn, Nils Billecke, Sapun H. Parekh, Markus Klapper and Klaus Müllen

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27363

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      A polarity reversal of a nanoparticle surface with a light-sensitive PEG-block-poly((1-pyrenyl methyl)glutamate) (PEG-b-PGlu(Pyr)) copolymer is presented. The copolymer is successfully applied as emulsifier in a nonaqueous emulsion polymerization of lactide. The hydrophobic pyrenyl methylene units are readily cleaved from the outer hydrophilic PGlu-block by UV irradiation. The initially hydrophobic particles can now be dispersed in aqueous medium without the need of additional surfactants.

  11. Articles

    1. Design of high-χ block copolymers for lithography

      William J. Durand, Gregory Blachut, Michael J. Maher, Stephen Sirard, Summer Tein, Matthew C. Carlson, Yusuke Asano, Sunshine X. Zhou, Austin P. Lane, Christopher M. Bates, Christopher J. Ellison and C. Grant Willson

      Article first published online: 30 AUG 2014 | DOI: 10.1002/pola.27370

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      Several silicon-containing block copolymers composed of styrene and its derivatives were investigated for lithographic applications. The interaction parameter (χ) of each material was estimated via two well-known techniques, demonstrating increases two to three times that of poly(styrene-block-4-trimethylsilylstyrene) upon appending various functional groups. Perpendicular-oriented thin films of BCPs were developed by reactive ion etching to demonstrate high aspect ratio patterns. Higher silicon-content components demonstrated greater etch resistance, and more strongly segregated BCPs improve pattern fidelity.

    2. Preparation and evaluation of a polymeric gel containing ionic liquid-functionalized MWCNTs as a novel class of organic solvent absorbent

      Ali Pourjavadi and Malihe Doulabi

      Article first published online: 28 AUG 2014 | DOI: 10.1002/pola.27372

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      Ionic liquid-functionalized MWCNTs consisting of vinyl immidazolium cations and lipophilic tetrafluoroborate counteranions were synthesized and used as a novel crosslinking agent for the preparation of a new absorbent gel. The prepared MWCNT-based polymeric gel (ILMPG) exhibits high organic solvent absorbency, fast organic solvent absorption rate, and good reusability. ILMPG does not swell in water and can potentially be used for cleaning oil and organic solvent spills on water.

    3. Tuning the energy gap of conjugated polymer zwitterions for efficient interlayers and solar cells

      Zachariah A. Page, Feng Liu, Thomas P. Russell and Todd Emrick

      Article first published online: 25 AUG 2014 | DOI: 10.1002/pola.27349

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      Six narrow energy gap conjugated polymer zwitterions (CPZs) comprised of diketopyrrolopyrrole (DPP) and iso-indigo (iIn) backbones with pendant sulfobetaine (SB) solubilizing chains were synthesized. Probing the electronic properties and surface-metal interactions of the CPZs revealed energy gaps from 1.7 to 1.2 eV, and a 0.9 eV reduction in the work function of Ag. As buffer layers in BHJ solar cells, these CPZs improve device power conversion efficiency from 1.6% without the CPZ to 6.7-7.7% with the CPZ interlayer.

  12. Rapid Communication

    1. Advanced photoresist technologies by intricate molecular brush architectures: Diblock brush terpolymer-based positive-tone photoresist materials

      Guorong Sun, Sangho Cho, Fan Yang, Xun He, Adriana Pavía-Sanders, Corrie Clark, Jeffery E. Raymond, Stanislav V. Verkhoturov, Emile A. Schweikert, James W. Thackeray, Peter Trefonas and Karen L. Wooley

      Article first published online: 22 AUG 2014 | DOI: 10.1002/pola.27362

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      The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top-down/bottom-up construction of advanced positive-tone photoresist materials. By selective partition the substrate adhesion, surface-active migration, and chemically-reactive deblocking functional compositions into the cylindrical polymer brush architectures, large-areas of vertical alignment of the polymers within thin films are realized. The bottom-up premeditated system enables effective top-down lithography to produce near-molecular pixel resolution (2–3 molecules) at low operation dosage.

  13. Articles

    1. Revisiting thiol-yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

      Johannes K. Sprafke, Jason M. Spruell, Kaila M. Mattson, Damien Montarnal, Alaina J. McGrath, Robert Pötzsch, Daigo Miyajima, Jerry Hu, Allegra A. Latimer, Brigitte I. Voit, Takuzo Aida and Craig J. Hawker

      Article first published online: 18 AUG 2014 | DOI: 10.1002/pola.27345

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      Polymer coupling reactions are some of the most challenging chemical transformations due to low end-group concentration, steric hindrance, and decreased reactivity. Thiol-yne chemistry is shown to be a near-quantitative and selective strategy for the coupling of pre-formed polymers to give block and graft copolymers. With aromatic alkynes under a wide range of conditions, specific mono-addition is achieved with efficiencies surpassing those of traditional thiol-ene chemistry.

    2. Influence of linkage chemistry on folding, self-assembly, and photoresponse of amphiphilic azobenzene main chain polymers

      Zhilin Yu and Stefan Hecht

      Article first published online: 14 AUG 2014 | DOI: 10.1002/pola.27344

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      Two types of amphiphilic polymers, composed of azobenzene repeat units in the main chain connected either via ethynylene or butadiynylene linkages and carrying (chiral) oligo(ethylene glycol) side chains, have been synthesized via Sonogashira–Hagihara or Glaser polycondensation. Solvent titration experiments reveal that both polymers fold into stable helices in a polar environment. While the ethynylene-bridged polymer (PAzoE) resembles the behavior of its oligomeric counterparts, introduction of the extended diacetylene unit strengthens π,π-stacking interactions in case of the butadiynylene-bridged polymer (PAzoB), leading to a pronounced aggregation tendency and suppressing photoisomerization in the folded state.

    3. Importance of unpaired electrons in organic electronics

      Jonathan D. Yuen, Mingfeng Wang, Jian Fan, Dennis Sheberla, Moureen Kemei, Natalie Banerji, Mariateresa Scarongella, Sebastian Valouch, Toan Pho, Rajeev Kumar, Eneida C. Chesnut, Michael Bendikov and Fred Wudl

      Article first published online: 11 AUG 2014 | DOI: 10.1002/pola.27321

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      PBBTPD, a low bandgap, ambipolar conjugated donor-acceptor polymer based on benzobisthiadiazole (BBT), is shown to possess an open-shell singlet ground state as well as a thermally accessible triplet state. Theoretical predictions have suggested that such behavior is due to the biradicaloid character of BBT. This biradicaloid structure is in each BBT moiety and therefore PBBTPD is in fact a polyradicaloid. These observations will aid in development of better n-type polymeric acceptors for organic semiconductor applications.

  14. Foreword

  15. Articles

    1. Synthesis of amphiphilic homopolymers with high chain end functionality by SET–LRP

      Shampa R. Samanta, Ruilong Cai and Virgil Percec

      Article first published online: 7 AUG 2014 | DOI: 10.1002/pola.27331

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      For the first time SET–LRP of two amphiphilic acrylates, 2-methoxyethyl acrylate up to [M]0/[I]0 = 1000 and di(ethylene glycol) 2-ethylhexyl ether acrylate up to [M]0/[I]0 = 200 with very good control of molecular weight and molecular weight distribution is demonstrated in a common organic solvent, trifluoroethanol at 25 °C. Analysis of the chain end functionality of the resulting polymers demonstrates the synthesis of near-perfect chain-end functional homopolymers. This facile method opens up attractive possibilities for the fast synthesis of polymers with complex architecture under mild reaction conditions from amphiphilic monomers.

    2. One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a “catalyst switch” strategy

      Junpeng Zhao, David Pahovnik, Yves Gnanou and Nikos Hadjichristidis

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27332

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      Two epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator using a strong phosphazene base promoter. An excess of diphenyl phosphate was introduced, followed by successive addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). Linear- and star-tetrablock quarterpolymers were prepared in one pot using this “catalyst switch” strategy.

  16. Rapid Communication

    1. Aspect ratio effect of nanorod surfactants on the shape and internal morphology of block copolymer particles

      Kang Hee Ku, Hyunseung Yang, Jae Man Shin and Bumjoon J. Kim

      Article first published online: 6 AUG 2014 | DOI: 10.1002/pola.27333

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      The effect of aspect ratio (AR) of nanorod (NR) surfactants on the shape and internal morphology of block copolymer (BCP) particles was systemically investigated using CuPt NRs with different AR values ranging from 1 to 15. The positioning of the NRs in the BCP particles was dependent strongly on their AR values, and it enabled the modulation of the interfacial properties at selective locations on the BCP particles, thus producing interesting morphological transition of the BCP particles.

  17. Articles

    1. Controlled cyclopolymerization of 4,5-disubstituted 1,7-octadiynes and its application to the synthesis of a dendronized polymer using Grubbs catalyst

      Hyeon Park, Ho-Keun Lee, Eun-Hye Kang and Tae-Lim Choi

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27317

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      Cyclopolymerization of 4,5-disubstituted 1,7-octadiyne using a third generation Grubbs catalyst is reported. With this highly reactive polymerization method, monomers with substituents varying from small ester to large dendron were successfully polymerized with rapid propagation rate.

  18. Rapid Communications

    1. Synthesis and characterization of novel amphiphilic super-H copolymers with linear–dendritic architecture

      Ivan Gitsov, Iliana V. Berlinova and Nikolay G. Vladimirov

      Article first published online: 1 AUG 2014 | DOI: 10.1002/pola.27318

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      Novel linear–dendritic super-H block copolymers are prepared by multistage synthetic process involving “living” polymerizations.

    2. Self-assembly and reassembly of fiber-forming dipeptides for pH-triggered DNA delivery

      Glenn R. Hafenstine, Dylan W. Domaille, Jennifer N. Cha and Andrew P. Goodwin

      Article first published online: 31 JUL 2014 | DOI: 10.1002/pola.27319

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      Hydrazone-based conjugates of PEG-dipeptide and DNA-dipeptide were designed to form stable vesicles at neutral pH, break apart at mildly acidic pH, and form large peptide fibers on release. Light scattering measurements showed that DNA-loaded vesicles of ∼80 nm were stable at pH 7.4 for 6 h and fell apart within 1 h at pH 5, with the DNA fully released from the formed fibers.

  19. Articles

    1. Bulk dispersion of single-walled carbon nanotubes in silicones using diblock copolymers

      Ryan C. Chadwick, Darryl Fong, Nicole A. Rice, Michael A. Brook and Alex Adronov

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27313

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      Supramolecular complexes of poly(3-decylthiophene)-block-polydimethylsiloxanes (P3DT-b-PDMS) with single-walled carbon nanotubes (SWNTs) enable homogeneous incorporation of SWNTs within a bulk silicone elastomer, resulting in a low percolation threshold. The block copolymer anchors SWNTs within the silicone elastomer, allowing repeated stretching and relaxation without degradation of conductivity.

  20. Highlight

    1. You have free access to this content
      Functional aqueous assemblies of linear-dendron hybrids

      Greg Whitton and Elizabeth R. Gillies

      Article first published online: 30 JUL 2014 | DOI: 10.1002/pola.27316

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      Recent progress on the development of aqueous assemblies of linear-dendron hybrids capable of performing functions is described. By engineering chemical functionalities in the linear or dendritic component, as well as their architectures, a wide variety of functions—including drug encapsulation, cell targeting, lectin binding, hydrogel formation, and catalysis—can be introduced. In addition, the assemblies can be designed to respond to a variety of stimuli including pH, temperature, light, and enzymes.

  21. Articles

    1. Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic liquids and ionogel properties

      Jun'ichi Nagasawa, Sonoko Wakahara, Hajime Matsumoto, Hideyuki Kihara and Masaru Yoshida

      Article first published online: 28 JUL 2014 | DOI: 10.1002/pola.27310

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      Positively charged polyelectrolytes with N,N′ -(trans-cyclohexane-1,4-diyl)dibenzamide linkages and varying spacer lengths have been synthesized and their ability to effect gelation for six ionic liquids and the properties of the resulting ionogels have been examined. The polymers gelatinize most of the tested ionic liquids at low concentrations (0.9-50 g/L). Gel-sol transition temperatures are dependent on the spacer length, while ionic conductivities of the various ionogels are near those of the neat ionic liquids and are not affected by spacer length.

  22. Rapid Communication

    1. You have free access to this content
      Kilogram scale inverse vulcanization of elemental sulfur to prepare high capacity polymer electrodes for Li-S batteries

      Jared J. Griebel, Guoxing Li, Richard S. Glass, Kookheon Char and Jeffrey Pyun

      Article first published online: 25 JUL 2014 | DOI: 10.1002/pola.27314

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      Synthetic conditions to prepare high sulfur content copolymers via inverse vulcanization on a kilogram scale is reported. By investigation of polymerization comonomer feed ratios, reaction temperature, and scale, the development of conditions to enabled the large scale synthesis of poly(sulfur-random-(1,3-diisopropenylbenzene) was conducted. We further demonstrated enhanced device performance of these sulfur copolymers as active cathode materials in Li-S batteries.

  23. Articles

    1. Synthesis of degradable molecular brushes via a combination of ring-opening polymerization and click chemistry

      Yi Shi, Xiaofeng Wang, Robert W. Graff, William A. Phillip and Haifeng Gao

      Article first published online: 23 JUL 2014 | DOI: 10.1002/pola.27307

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      Molecular brushes with an acid-degradable backbone and densely-grafted side chains (2 side chains per backbone repeating unit) are synthesized using an efficient grafting-onto method. The incorporated side chains vary from homopolymers to block copolymers and grafted polymers, and the produced molecular brushes can be degraded completely into linear polymers. When a mixture of side chains are used, the amphiphilic hetero-grafted molecular brushes can assemble in water and form either spherical micelles or hollow vesicles depending on sample compositions.

    2. Facile synthesis of high-molecular-weight acid-labile polypeptides using urethane derivatives

      Shirley Wong and Young Jik Kwon

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27320

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      Preparation of acid-labile polypeptides by conventional methods, which polymerize unstable, moisture-sensitive amino acid monomers under highly restrictive conditions, has been challenging. A new method is reported that allows convenient synthesis of stable monomers and fast polymerization under easily applicable conditions, yielding high-molecular-weight acid-labile polypeptides with narrow polydispersity. The highly facile strategy demonstrated in this study could contribute to synthesizing stimuli-responsive peptide-based biomaterials for various biomedical applications.

    3. Synthetic control over the dynamics of mesoscaled cargo release from colloidal polymer vectors inside live cells

      Harvind S. Chahal, Dev S. Chahal, Patrick M. McBride and Brett A. Helms

      Article first published online: 22 JUL 2014 | DOI: 10.1002/pola.27312

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      Dynamic complementarity between colloidal polymer vectors and their electrostatically adsorbed cargo is a critical parameter that influences the rate of cargo release once inside cells. Where endogenous macromolecules within the cytosol favorably compete for adsorption sites at the vector surface, cargo can be efficiently released and trafficked to intracytosolic targets.

    4. Synthesis and characterization of double hydrophilic block copolymers containing semi-rigid and flexible segments

      Alice M. Savage, Elizabeth Ullrich, Stacey M. Chin, Zachary Kiernan, Caitlyn Kost and S. Richard Turner

      Article first published online: 15 JUL 2014 | DOI: 10.1002/pola.27296

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      Two sterically crowded stilbene comonomers, 3-methyl-(E)-stilbene (3MSti) and 4-(diethylamino)-(E)-stilbene, are polymerized separately with maleic anhydride using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques. RAFT agent compatibilities and reaction kinetics for each comonomer system are compared. Double hydrophilic block copolymers are synthesized from these copolymers and converted to polyelectrolytes. The isoelectric point and dissociation behavior of the polyelectrolytes are determined using ζ-potential and acid-base titrations, respectively.

    5. ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization

      Natalia A. Agudelo, Andrea M. Elsen, Hongkun He, Betty L. López and Krzysztof Matyjaszewski

      Article first published online: 9 JUL 2014 | DOI: 10.1002/pola.27300

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      A series of ABA triblock copolymers were synthesized utilizing two polymerization techniques, polycondensation and atom transfer radical polymerization (ATRP). The choice of polymerization mechanisms results in block copolymers with unique molecular weight distributions the center of these triblock copolymers are disperse, resulting from polycondensation while the outside blocks have narrow molecular weight distribution due to the control afforded from ATRP.

  24. Highlight

    1. Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 20 JUN 2014 | DOI: 10.1002/pola.27279

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      Just like any other method of polymerization, direct arylation polymerization (DArP) produces defects in polymer structure, which have a strong impact on polymer properties. Therefore, it is important for polymer scientists to understand what causes the defect formation and how to control them. DArP produces four major classes of defects, and here we discuss in detail the origin of defects, their influence on polymer properties and the available methods to control them.


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