Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 53 Issue 16

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. 1 - 74
  1. Articles

    1. 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.

    2. 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.

    3. Novel isoindigo-based conjugated polyelectrolytes: Synthesis and fluorescence quenching behavior with water-soluble poly(p-phenylenevinylene)s

      Chun Kou, Xiaolong He, Xueyu Jiang, Yifeng Ni, Ling Liu, Changxin Huangfu and Kuan Liu

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27711

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      Two novel ID-based conjugated polyelectrolytes (+)-PIDPV and (−)-PIDPV were synthesized and both polymers exhibit broad absorption band in the visible region. The fluorescence emission of (+)-PPV can be quenched by the addition of (−)-PIDPV at a very low concentration with KSV =1.01 × 106 M−1 while (−)-PPV gives a larger constant with KSV =1.71 × 106 M−1 in the presence of (+)-PIDPV. The efficient quenching effect is governed by various mechanisms while dynamic quenching is the leading factor. The fluorescence of PPVs is also quenched by the oppositely charged PIDPV in the solid state.

    4. Biocompatible amphiphilic conetwork based on crosslinked star copolymers: A potential drug carrier

      Haiye Wang, Aiwen Qin, Xiang Li, Xinzhen Zhao, Dapeng Liu and Chunju He

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27721

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      Novel “core-first” star polymer-based conetworks were successfully fabricated via sequential atom transfer polymerization. The amphiphilic conetworks (APCNs) exhibit unique swelling behavior, excellent mechanical properties, distinct phase separation, and good cytocompatibility, which are suitable for sustained controlled release of choline theophyllinate where the release rate can be regulated by varying the hydrophilic (HI) composition and crosslinking density. The overall results suggest that APCN is a promising candidate as a drug carrier.

    5. Synthesis of new optically active α,α′,β-trisubstituted-β-lactones as monomers for stereoregular biopolyesters

      Rima Belibel and Christel Barbaud

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27724

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      The use of biodegradable and bioassimilable stereopolymers is innovative for temporary therapeutic applications. Stereopolyesters derived from malic acid were synthesized by anionic polymerization from new optically active α,α′,β-trisubstituted-β-lactones as monomers. The total synthesis and characterization of a series of design lactones and one isotactic homopolyester are described in detail.

    6. Random propene/4-methyl-1-pentene copolymers synthesized with C2 symmetric highly isospecific metallocenes

      Maria Carmela Sacchi, Simona Losio, Luigi Fantauzzi, Paola Stagnaro, Roberto Utzeri and Maurizio Galimberti

      Article first published online: 30 JUN 2015 | DOI: 10.1002/pola.27725

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      Random propene-based copolymers with a 1-olefin such as 4-methyl-1-pentene (Y), within a wide range of compositions, are prepared with the highly isospecific single site catalyst, rac-CH2(3- t BuInd)2ZrCl2. This finding is against what is acknowledged in the field and provides a novel strategy for the preparation on a large scale of random propene-based copolymers by properly selecting the metallocene/comonomer combination.

    7. Thermoresponsive polymersome from a double hydrophilic block copolymer

      Prithankar Pramanik and Suhrit Ghosh

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27735

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      Neither micelle nor gel, well-defined nano vesicles were prepared by thermally triggered self-assembly of a PEO-b-PNIPAm copolymer having an appropriate hydrophobic/hydrophilic balance.

  2. Original Articles

    1. Synthesis of poly(2-oxazoline)s with side chain methyl ester functionalities: Detailed understanding of living copolymerization behavior of methyl ester containing monomers with 2-alkyl-2-oxazolines

      Petra J. M. Bouten, Dietmar Hertsen, Maarten Vergaelen, Bryn D. Monnery, Saron Catak, Jan C. M. van Hest, Veronique Van Speybroeck and Richard Hoogenboom

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27733

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      Poly(2-oxazoline)s can be prepared by cationic ring opening polymerization. Kinetic studies of the homo- and copolymerization of methyl ester containing 2-oxazoline monomers were performed showing a faster propagation for the methyl ester containing monomers than for alkyl monomers. Surprisingly in copolymerization these rates are inversed, yielding gradient copolymers. These observations are supported by computational studies, confirming that methyl ester groups increase nucleophilicity of the living chain end.

  3. Articles

    1. Influence of functionality on direct arylation of model systems as a route toward fluorinated copolymers via direct arylation polymerization (DArP)

      Francesco Livi, Nemal S. Gobalasingham, Eva Bundgaard and Barry C. Thompson

      Article first published online: 29 JUN 2015 | DOI: 10.1002/pola.27728

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      The synthesis of a defect-free fluorinated copolymer through direct arylation polymerization of a thiophene-containing monomer and a highly fluorinated benzene monomer is reported. A small molecule direct arylation screening on similar substrates is carried out in order to obtain the best conditions for the polymerizations reaction. The functionalization of the monomers has a strong influence on the product outcome, both in case of small molecules and copolymers.

    2. Enhanced spin capturing polymerization: Numerical investigation of mechanism

      Sergey V. Nikitin, Dmitriy A. Parkhomenko, Mariya V. Edeleva and Elena G. Bagryanskaya

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27723

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      Simulations of kinetics of enhanced spin capturing polymerization were performed to reveal key factors that affect the parameters of the polymer obtained by this technique. Criteria for success were formulated allowing for an estimation of polymerization behavior prior to the experiment.

    3. A facile method to synthesize high-molecular-weight biobased polyesters from 2,5-furandicarboxylic acid and long-chain diols

      Vasilios Tsanaktsis, George Z. Papageorgiou and Dimitrios N. Bikiaris

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27730

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      Biobased 2,5-furandicarboxylate polyesters with long-chain diols are synthesized successfully using the dimethylester of 2,5-dicarboxylic acid and diols containing 8–12 methylene groups. Because of the high boiling point of these diols and their high distillation difficulty, a new method was proposed to produce polyesters with high molecular weight. All polyesters are semicrystalline materials with appropriate mechanical properties, which depend on the methylene group number.

    4. Substituent effect of N-aryl-N′-pyridyl ureas as thermal latent initiators on ring-opening polymerization of epoxide

      Naoyuki Makiuchi, Atsushi Sudo and Takeshi Endo

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27726

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      A series of N-aryl-N′-pyridyl ureas having various substituent on the aryl moiety were synthesized and studied as thermally latent initiators for the ring-opening polymerization of epoxides. DSC measurement for formulations comprised of DGEBA and the ureas clarified that relationship between the reaction temperature and the electron density of the aromatic ring of the ureas.

    5. Thermo- and pH-sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

      Christophe Pottier, Gaëlle Morandi, Virginie Dulong, Zied Souguir, Luc Picton and Didier Le Cerf

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27729

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      Synthesis and characterization of multiresponsive P(AA-co-tBA)-b-PPO-b-P(AA-co-tBA) triblock copolymers are presented. These copolymers were elaborated by atom transfer radical polymerization (ATRP) and partial hydrolysis of tert-butyl acrylate (tBA) moieties providing both control on the outer blocks length and on the acrylic acid (AA)/tBA composition. The self-assembly of the triblock copolymers in aqueous solution is demonstrated to be dependent on the hydrophilic/lipophilic composition. Moreover, copolymers show thermo- and pH-sensitive properties due to deshydratation of poly(propylene oxide) (PPO) block and ionization of PAA blocks.

    6. Control through monomer placement of surface properties and morphology of fluoromethacrylate copolymers

      Ao Chen, Idriss Blakey, Kevin S. Jack, Andrew K. Whittaker and Hui Peng

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27731

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      The effect of polymer placement on surface energy and bulk morphology was investigated for block and statistical copolymers of methyl methacrylate and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (F3MA). Incorporation of the fluoromonomer lowered the surface energy, and the decrease was more significant for the polymer with block structure. The bulk phase structure for the block copolymers ranged from cylindrical to spherical depending on the copolymer composition. A value of the solubility parameter for polymers of F3MA was determined.

    7. Synthesis of polyphoscphodiesters by ring-opening polymerization of cyclic phosphates bearing allyl phosphoester protecting groups

      Benoït Clément, Daniel G. Molin, Christine Jérôme and Philippe Lecomte

      Article first published online: 25 JUN 2015 | DOI: 10.1002/pola.27732

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      Anionic aliphatic polyphosphodiesters are synthesized by a new strategy based on the ring-opening polymerization of a cyclic phosphate bearing an allyl phosphoester protecting group. The deprotection is achieved by reaction with sodium benzenethiolate in the absence of any detectable degradation. No transition metal is involved at any step of the process (the synthesis of the monomer, the polymerization and the final deprotection).

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      Synthesis, Characterization, and thermoresponsive properties of Helical Polypeptides Derivatized from Poly(γ−4-(3-chloropropoxycarbonyl)benzyl-L-glutamate)

      Yong Deng, Xi Wang, Qiulin Yuan, Mengxiang Zhu, Ying Ling and Haoyu Tang

      Article first published online: 23 JUN 2015 | DOI: 10.1002/pola.27708

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      Two types of helical polypeptides bearing oligo-ethylene-glycol (OEG) groups or 1-butylimidazolium salts have been prepared from poly−4-(3-chloropropoxy-carbonyl)benzyl-L-glutamate) with high grafting densities. Polymers bearing 1-butylimidazolium and I counter-anions exhibited reversible UCST-type transitions in water. Polymers bearing OEG3 side-chains showed reversible LCST-type phase transition behaviors in water and reversible UCST-type phase transition behaviors in various organic solvents.

    9. The effect of molecular weight on the separation of semiconducting single-walled carbon nanotubes using poly(2,7-carbazole)s

      Nicole A. Rice, Ayyagari V. Subrahmanyam, Scott E. Laengert and Alex Adronov

      Article first published online: 19 JUN 2015 | DOI: 10.1002/pola.27715

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      The molecular weight of poly(2,7-carbazole)s has an impact on their ability to selectively disperse semiconducting single-walled carbon nanotubes (SWNTs) in THF. Molecular weights below 30 kDa result in dispersions containing mixtures of semiconducting and metallic structures, while above 30 kDa, a high degree of selectivity for semiconducting SWNTs is observed.

  4. Rapid Communication

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      Combined atom-transfer radical polymerization and ring-opening polymerization to design polymer–polypeptide copolymer conjugates toward self-aggregated hybrid micro/nanospheres for dye encapsulation

      Anupam Saha, Tapas K. Paira, Mrinmoy Biswas, Somdeb Jana, Sanjib Banerjee and Tarun K. Mandal

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27713

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      A designed orthogonal dual initiator is employed to construct poly(methyl methacrylate)-block-polytyrosine copolymer conjugates via the combination of atom-transfer radical polymerization of methyl methacrylate, “click” chemistry and ring-opening polymerization of tyrosine–α-amino acid N-carboxyanhydride monomer. The polymer–polypeptide conjugate undergoes self-aggregation in dimethylformamide to produce hybrid micro/nanospheres owing to the formation of composite micelle as evidenced from field emission scanning electron microscopy and dynamic light scattering study. A simple solution-based approach is described to encapsulate an organic dye (Rhodamine-6G) into the aggregated hybrid micro/nanospheres.

  5. Articles

    1. Utilization of poly(vinylchloride) and poly(vinylidenefluoride) as macroinitiators for ATRP polymerization of hydroxyethyl methacrylate: Electroanalytical and graft-copolymerization studies

      Sonia Lanzalaco, Alessandro Galia, Flavia Lazzano, Rosalia Rita Mauro and Onofrio Scialdone

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27717

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      The utilization of poly(vinylchloride) and poly(vinylidenefluoride) as macroinitiators for atom transfer radical polymerization of hydroxyethyl methacrylate was studied. Electroanalytical investigations and “grafting from” experiments suggest that both C[BOND]Cl and C[BOND]F bonds can be cleaved by Cu based catalytic systems to generate macroradicals. Lower grafting levels were obtained in the case of the fluorinated polymer probably as a consequence of the higher strength of the C[BOND]F bond.

    2. Poly[N-(10-oxo-2-vinylanthracen-9(10H)-ylidene)cyanamide] as a novel cathode material for li-organic batteries

      Daniel Schmidt, Bernhard Häupler, Christian Stolze, Martin D. Hager and Ulrich S. Schubert

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27716

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      Poly[N-(10-oxo-2-vinylanthracen-9(10H)-ylidene)cyanamide] as a novel cathode material for Li-organic batteries The application of polymers bearing N-(10-oxo-anthracen-9(10H)-ylidene)cyanamide units as electrode material in lithium organic batteries enables a charge/discharge device featuring a cell potential of 2.3 V, a theoretical capacity of 207 mAh/g and a good stability (100 cycles, 15% loss).

    3. Versatile soluble oligomeric styrene supports for peptide synthesis

      Venkataramana Erapalapati and Nandita Madhavan

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27714

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      Soluble styrene oligomers incorporated with high loading capacities are used to load a variety of amino acids in 59–85% yields. The supports are used to synthesize hexapeptides in 50% yields using only 2 equivalents of coupling reagents. The support synthesis is modular enabling incorporation of any styrene derived attachment site onto the highly soluble oligomer backbone.

  6. Rapid Communication

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      X-ray absorption fine structure study on the role of solvent on polymerization of 3-hexylthiophene with solid FeCl3 particles

      Tomoyasu Hirai, Masanao Sato, Makoto Kido, Yusuke Nagae, Katsuhiro Kaetsu, Yudai Kiyoshima, Shota Fujii, Tomoyuki Ohishi, Kevin L. White, Yuji Higaki, Yasutake Teraoka, Maiko Nishibori, Kazutaka Kamitani, Kenji Hanada, Takeharu Sugiyama, Ryuichi Sugimoto, Kazuhiko Saigo, Ken Kojio and Atsushi Takahara

      Article first published online: 17 JUN 2015 | DOI: 10.1002/pola.27720

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      The effect of solvent on the polymerization of 3-hexylthiophene with FeCl3 was evaluated using time-dependent partial fluorescence yield X-ray absorption fine structure measurements. FeCl3 acts as a catalyst when the reaction is performed in CHCl3, whereas it behaves as an oxidant in hexane.

  7. Articles

    1. Radical Polymerization of methacrylates with an adamantane-like rigid core derived from naturally occurring myo-inositol

      Shusuke Okamoto, Shohei Onoue, Mami Muramatsu, Shimpei Yoshikawa and Atsushi Sudo

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27705

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      myo-Inositol orthoester was converted into tri- and dimethacrylate monomers with a rigid adamantane-like core. The radical polymerization of trimethacrylate and its copolymerization with methyl methacrylate yielded networked polymers that exhibited higher thermal stability than those of networked polymers with a less rigid cyclohexane structure at the crosslinking points. Analyzing the radical polymerization of dimethacrylate provided an insight into the polymer structure. The process advanced in a cyclopolymerization manner to yield polymers with high glass transition temperature of up to 285°C through the incorporation of rigid cyclic structures into the repeating unit.

  8. Rapid Communications

    1. Triptycene-based microporous polymer incorporating thioamide functionality: Preparation and gas storage properties

      Lei Liu, Yijie Xia and Jie Zhang

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27709

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      Triptycene-based microporous polymer was functionalized with thioamide moieties via postpolymerization. Gas adsorption experiments indicate that the modification leads to a reduction in the BET surface area of the polymer, from 1640 m2 g−1 for the parent TMP to 207 m2 g−1; however, the resulting microporous polymer still possesses high H2 uptake capacity, reaching 101.1 cm3 g−1 (0.9 wt %) at 1.0 bar and 77 K, along with relatively high selectivity toward CO2 over CH4 and N2.

  9. Articles

    1. Oxime functionalization strategy for iodinated poly(epsilon-caprolactone) X-ray opaque materials

      Samantha E. Nicolau, Lundy L. Davis, Caroline C. Duncan, Timothy R. Olsen, Frank Alexis, Daniel C. Whitehead and Brooke A. Van Horn

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27706

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      A novel "Click" postpolymerization strategy for the preparation of x-ray opaque polycaprolactone is presented. The final functional copolymer products were achieved by (1) a random copolymerization with a functional caprolactone comonomer, (2) deprotection of the comonomer repeat units, and (3) the acid-catalyzed oxime postpolymerization ligation of a hydroxylamine bearing iodine. Rigorous structural and thermal characterization were performed to confirm the identity and functionality of the radio-opaque materials.

    2. The effect of amide solvent structure on the direct arylation polymerization (DArP) of 2-Bromo-3-hexylthiophene

      Andrey E. Rudenko and Barry C. Thompson

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27712

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      The effect of amide solvent structure on the properties of DArP P3HT is explored. The results indicate that the amide structure must be acyclic and contain alkyl substituents of sufficient, but not excessive steric bulk to promote efficient polymerization. The resulting polymers contain a minimal content of structural defects and possess attractive physical properties.

    3. Degradable poly(ester triazole)s based on renewable resources

      Khalid Hakkou, Manuel Bueno-Martínez, Inmaculada Molina-Pinilla and Juan A. Galbis

      Article first published online: 16 JUN 2015 | DOI: 10.1002/pola.27710

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      Novel degradable linear polymers have been prepared from carbohydrates such as glucose, arabinose, and erythrose by copper(I)-catalyzed alkyne-azide cycloaddition click polymerization. These polymers contain in their repeating units two or more free secondary alcohol functions which were used to prepare some network structures by crosslinking reaction with hexamethylene diisocyanate.

  10. Corrigendum

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      Corrigendum: Polymerizability of exo-methylene-lactide towards vinyl addition and ring opening

      Garret M. Miyake, Yuetao Zhang and Eugene Y.-X. Chen

      Article first published online: 15 JUN 2015 | DOI: 10.1002/pola.27704

      This article corrects:

      Polymerizability of Exo-methylene-lactide toward vinyl addition and ring opening

      Vol. 53, Issue 12, 1523–1532, Article first published online: 2 APR 2015

  11. Articles

    1. Poly(thieno[3,4-b]-1,4-oxathiane) and poly(3,4-ethylenedioxythiophene-co-thieno[3,4-b]-1,4-oxathiane)/poly(styrene sulfonic sodium): Preparation, characterization, and optoelectronic performance

      Zhipeng Wang, Daize Mo, Shuai Chen, Jingkun Xu, Baoyang Lu, Qinglin Jiang, Zilan Feng, Jinhua Xiong and Shijie Zhen

      Article first published online: 12 JUN 2015 | DOI: 10.1002/pola.27698

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      A new PEDOT sulfur analog/PSS complex was chemically synthesized and copolymerized with EDOT in PSS yielding poly(EOTT−co−EDOT)/PSS. The electrochemical and optoelectronic properties of the complexes were evaluated. The copolymer complexes showed favorable electrochromic performance with high coloration efficiencies (375 cm2/C), low switching voltages (−0.8 to +0.6 V), decent contrast ratios (45%), moderate response time (1.0 s), excellent stability, and color persistence. The copolymer material is a promising candidate for organic electronics.

    2. Facile synthesis of poly(DMC-co-HPA) hydrogels via infrared laser ignited frontal polymerization and their adsorption–desorption switching performance

      Yang Li, Shengyang Yang, Cai-Feng Wang and Su Chen

      Article first published online: 12 JUN 2015 | DOI: 10.1002/pola.27701

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      A series of poly(DMC-co-HPA) hydrogels are successfully fabricated via infrared laser ignited frontal polymerization for the removal of heavy metal pollutants in aqueous solution. Kerosene and polyoxyethylene sorbitan monolaurate have been introduced into the hydrogel networks to endow the hydrogel with ability to float on the surface for convenient collection after intaking metal ions. This strategy not only greatly promotes efficiency in wastewater treatment, but also offers an available avenue towards the production of custom-made structures in the hydrogel morphology that bear predetermined performance for diverse applications.

    3. Synthesis and radical polymerization of methacrylate endowed with bicyclobis(γ-butyrolactone) moiety through methylene linker

      Ryu Yamasaki, Atsushi Sudo and Takeshi Endo

      Article first published online: 12 JUN 2015 | DOI: 10.1002/pola.27707

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      A series of novel methacrylates bearing a highly polar and rigid bicyclobis(γ-butyrolactone) (BBL) moiety were synthesized and radically polymerized to afford the corresponding poly(methacrylate)s. The incorporation of BBL structure in the side chain endowed the polymers with good solubility in aprotic polar solvents and high glass transition temperatures up to 138 °C.

  12. Original Articles

    1. Core–shell structure PEO/CS nanofibers based on electric field induced phase separation via electrospinning and its application

      Guangkai Chen, Dawei Fang, Kemin Wang, Jun Nie and Guiping Ma

      Article first published online: 6 JUN 2015 | DOI: 10.1002/pola.27702

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      PEO/chitosan core/shell nanofiber was prepared via electrospinning process with the assistance of electric field (E1) induced phase separation. The positive charged chitosan was moving along the direction of electric field towards surface forming core/shell electrospinning jet. Simultaneously, a small potential (E2) was formed due to accumulation of positive charged chitosan. As electrospinning jet ejected, nanofiber was solidified as the solvent volatilized before chitosan was induced to move back by E2.

  13. Articles

    1. Synthesis and structure-optoelectronic property relationships of a series of PPV and SFTV derived polymers

      Tanya M. S. David, Wondwossen Arasho and Sam-Shajing Sun

      Article first published online: 6 JUN 2015 | DOI: 10.1002/pola.27703

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      3,6-Carbazole-based derivatives of polyphenylene vinylene (PPV) and sulfone thienylene vinylene (SFTV) polymers exhibited better thermal and electronic stability and higher band gaps than benzene-based PPV and SFTV. This research focuses on obtaining pertinent information about the structure-property relationships of PPV-derived and SFTV-derived conjugated polymer blocks for developing potential supra-molecular high efficiency optoelectronics polymer-based devices.

    2. Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

      Lale Nur Atici, Erhan Demirel, Umit Tunca, Gurkan Hizal and Hakan Durmaz

      Article first published online: 4 JUN 2015 | DOI: 10.1002/pola.27697

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      A well-defined poly(oxanorbornene imide) (PONB) was prepared and reacted with bromine yielding PONB-Br which was further reacted with acrylate, epoxy and poly(ethylene glycol) (PEG) functionalized 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) under Cu(0)/CuBr/PMDETA catalyst condition in N,N-dimethylformamide (DMF) at room temperature overnight affording PONB-acrylate, PONB-epoxy and PONB-PEG through the nitroxide radical coupling (NRC) reaction.

    3. Synthesis and crosslinking of hyperbranched poly(n-nonyl acrylate) to form organogels

      Yangtian Lu, Dibyendu Debnath, R. A. Weiss and Coleen Pugh

      Article first published online: 3 JUN 2015 | DOI: 10.1002/pola.27700

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      (2-Bromo-n-nonan-1-oxycarbonyl)ethyl acrylate was homopolymerized and copolymerized by atom transfer radical polymerization (ATRP) and activator generated by electron transfer (AGET) ATRP to produce soluble polymers. The resulting hyperbranched (co)polymers undergo very efficient radical–radical crosslinking reaction by atom transfer radical coupling, resulting in hard plastic particles from the homopolymer of (2-bromo-n-nonan-1-oxycarbonyl)ethyl acrylate synthesized in bulk. Crosslinked organogels that swell in THF were formed when the rate of crosslinking decreased using acetonitrile solutions.

    4. Soft matter nanoparticles with reactive coronal pentafluorophenyl methacrylate residues via non-polar RAFT dispersion polymerization and polymerization-induced self-assembly

      Yiwen Pei, Janina-Miriam Noy, Peter J. Roth and Andrew B. Lowe

      Article first published online: 2 JUN 2015 | DOI: 10.1002/pola.27696

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      The concept of non-polar polymerization-induced self-assembly has been used for the synthesis of soft matter nanoparticles with spherical, worm, and vesicular morphologies containing reactive pentafluorophenyl methacrylate (PFPMA) in the nano-object coronae. The reaction of the PFPMA repeat units of the nanoparticles with small molecule primary amines yielded a new family of nanoparticles containing interesting surface-bound functionality.

    5. A New D–A conjugated polymer P(PTQD-BDT) with PTQD acceptor and BDT donor units for BHJ polymer solar cells application

      M. L. Keshtov, S. A. Kuklin, F. C. Chen, A. R. Khokhlov, Rajnish Kurchania and G. D. Sharma

      Article first published online: 29 MAY 2015 | DOI: 10.1002/pola.27699

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      A donor–acceptor copolymer P(PTQD0BDT) comprising of weak a BDT unit and strong PTQD unit was synthesized and used as a donor for the fabrication of bulk heterojunction (BHJ) polymer solar cells. The BHJ solar cell with optimized P(PTQD-BDT): PC71BM (1:2) active layer processed with 3% v DIO/CF showed power conversion efficiency of 5.55%.

    6. Reduction-cleavable hyperbranched polymers with limited intramolecular cyclization via click chemistry

      Heng Chen, Jiqiong Jia, Xiao Duan, Zhen Yang and Jie Kong

      Article first published online: 28 MAY 2015 | DOI: 10.1002/pola.27694

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      Reduction-cleavable hyperbranched polymers with limited intramolecular cyclization were achieved via click chemistry. The rigid triazole units generated from CuAAC click chemistry limited and reduced the intramolecular cyclization as well as the disulfide bonds introduced by A2 monomer gave the reduction-cleavable feature of the resulting hyperbranched polymers. The reduction-cleavable hyperbranched poly(ester triazole)s with limited intramolecular cyclization are expected to possess potential in the application of stimuli-responsive anticancer drug nanocarriers.

  14. Rapid Communication

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      A multistimuli-responsive supramolercular polymer constructed by crown ether-based molecular recognition and disulfide bond connection

      Hu Wang, Pi Wang, Hao Xing, Ning Li and Xiaofan Ji

      Article first published online: 27 MAY 2015 | DOI: 10.1002/pola.27693

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      We report a novel multistimuli-responsive supramolecular polymer constructed by a bis(benzo-21-crown-7)-based AA monomer containing a disulfide bond and a bis(dialkylammonium salt)-based BB monomer. Interestingly, the responsivenesses of this supramolarcular polymer are not only from the stimuli-responsive noncovalent interactions but also from the stimuli-responsive disulfide bond.

    2. Evolution of ppm amount of Ru(III) complexes for effective living radical polymerization of MMA

      Xiangxiong Chen, Thi Thuy Duong Nguyen, Mohd Yusuf Khan, Likai Xia, Dan He, Seung Woo Lee and Seok Kyun Noh

      Article first published online: 27 MAY 2015 | DOI: 10.1002/pola.27671

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      Three half-metallocene ruthenium(III) complexes, [(Cp*RuCl2)PPh2R] (R = C6H4–OCH3,C6H5, and C5H5N were prepared. These Ru(III) complexes polymerized MMA successfully via ATRP in the absence of any reducing agent or free radical initiator. All of three complexes produced a linear relationship between ln[Mn]0/[Mn] versus the reaction time and the living properties through a linear increase in molecular weight versus conversion. Especially, well-defined PMMA and high initiation efficiency were obtained in the presence of 10 ppm catalysts.

  15. Articles

    1. Functionalized PEG-b-PAGE-b-PLGA triblock terpolymers as materials for nanoparticle preparation

      Justyna A. Czaplewska, Tobias C. Majdanski, Markus J. Barthel, Michael Gottschaldt and Ulrich S. Schubert

      Article first published online: 22 MAY 2015 | DOI: 10.1002/pola.27674

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      The poly(ethylene glycol)-block-poly(allyl glycidyl ether) as well as their copolymers with poly(lactide-co-glycolide) are prepared by introduction of a primary OH group and subsequent ring-opening polymerization. The polymers are further functionalized via thiol-ene reaction. Spherical particles with diameters around 200 nm and a relatively low PDIparticle value of 0.03–0.1 could be obtained from the functional amphiphilic block copolymers (DLS and SEM). The obtained nanoparticles represent promising candidates for drug delivery studies.

    2. Ru(II)(tpy)2-functionalized hydrogels: Synthesis, reversible responsiveness, and coupling with the belousov-zhabotinsky reaction

      Hongwei Zhou, Yan Yang, Guohe Xu, Weixing Chen, Wenzhi Zhang, Qiguan Wang, Zhaohui Zheng and Xiaobin Ding

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27690

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      Ru(II)(Tpy)2-functionalized hydrogels are designed and prepared, the reversible redox responsiveness of the synthetic hydrogels is investigated, the occurrence of the BZ reaction in the hydrogel networks is demonstrated, and the self-oscillating properties of the BZ reaction are studied.

    3. Norbornene derivatives from a metal-free, strain-promoted cycloaddition reaction: New building blocks for ring-opening metathesis polymerization reactions

      Christopher E. Hobbs, Binhong Lin and Thomas Malinski

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27691

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      A facile 1,3-dipolar cycloaddition between azides and norbornadiene is used for the preparation of new monomers for ring-opening metathesis polymerization (ROMP) reactions. These species can be obtained under solvent-and catalyst-free reaction conditions and copolymerized with other norbornenes to provide new, functionalized polymers. Further polymer functionalization can be obtained through a thermal loss of N2.

    4. Novel chiral PEDOTs for selective recognition of 3,4-dihydroxyphenylalanine enantiomers: Synthesis and characterization

      Liqi Dong, Baoyang Lu, Xuemin Duan, Jingkun Xu, Dufen Hu, Kaixin Zhang, Xiaofei Zhu, Hui Sun, Shouli Ming, Zhipeng Wang and Shijie Zhen

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27695

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      This article reports two novel compounds of side-chain functionalized 3,4-ethylenedioxythiophenes (EDOTs), that is, (2R)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((R)-EDTM-PP) and (2S)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((S)-EDTM-PP). The new compounds can be employed as chiral electrodes to successfully recognize 3,4-dihydroxyphenylalanine (DOPA) enantiomers.

    5. Synthesis and characterization of benzimidazolium-functionalized polysulfones as anion-exchange membranes

      María Teresa Pérez-Prior, Alejandro Várez and Belén Levenfeld

      Article first published online: 21 MAY 2015 | DOI: 10.1002/pola.27692

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      A series of benzimidazolium-functionalized polysulfones were synthesized and characterized. The electrochemical behavior of the resulting anion-exchange membranes showed a clear dependence with the degree of chloromethylation of polysulfone. Thus, the ionic conductivity increased more than two orders of magnitude when the degree of chloromethylation increased from 40 to 140%. In addition, the presence of benzimidazolium groups instead of the widely used quaternary ammonium ones improved the ionic conductivity of the polymeric membranes.

    6. Boron subphthalocyanine polymers: Avoiding the small molecule side product and exploring their use in organic light-emitting diodes

      Benoît H. Lessard, Kathleen L. Sampson, Trevor Plint and Timothy P. Bender

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27685

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      The synthesis of boron subphthalocyanine (BsubPc)-containing polymers, while circumventing the formation of a known side-product, is described. The resulting BsubPc polymers are characterized by electrochemistry, photoluminescence spectroscopy, and even used as an active component in preliminary polymer-based organic light-emitting diodes. These polymer characterizations and device integration represent a first for BsubPc polymers.

    7. Synthesis of hyperbranched polyacetals via an + b2-type polyaddition (n = 3, 8, 18, and 21): Candidate resists for extreme ultraviolet lithography

      Hiroto Kudo, Shuhei Matsubara, Hiroki Yamamoto and Takahiro Kozawa

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27686

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      Hyperbranched polyacetals were synthesized by means of An + B2-type polyaddition reaction (n = 3, 8, 18, and 21). The physical properties, including solubility, thermal stability, and film-forming ability, and the photo-induced degradation reactivity under ultraviolet (UV) exposure and solubility-switch using an extreme UV exposure tool were consistent with potential applicability of poly(THPE-co-BVOC) and poly(CRA[4]-co-BVOC) as next-generation photo-resist materials.

  16. Rapid Communication

    1. Facile synthesis of formaldehyde-based polyether(-carbonate) polyols

      Jens Langanke, Jörg Hofmann, Christoph Gürtler and Aurel Wolf

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27687

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      Paraformaldehyde (pFA) was utilized as abundant building block to synthesize liquid and remarkably stable pFA-poly(alkoxy) and pFA-poly(alkoxy)(carbonate) triblock polyols by graft oligomerization of epoxides and variable amounts of CO2. The resulting tailor-made oligo diols are highly interesting precursors: They are partially made from alternative feedstock and are well suited as starting material for state-of-the-art polyurethane chemistry. Moreover, this study demonstrates the general feasibility of a novel polyether polyol process with a significantly reduced epoxide demand.

    2. Facile synthesis of fluorene-based π-conjugated polymers via sequential bromination/direct arylation polycondensation

      Hitoshi Saito, Junpei Kuwabara and Takaki Kanbara

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27689

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      The synthesis of fluorene-based π-conjugated polymers via sequential bromination and Pd-catalyzed direct arylation polycondensation was demonstrated; the protocol allows dual functionalization of each aromatic monomer in one-pot fashion. This synthetic protocol afforded the corresponding polymers with high molecular weights in good yields (up to yield 80%, Mn 34,500).

  17. Articles

    1. Synthesis of polycarbosilanes having sugar-derived structures as novel materials for cell cultivation

      Kozo Matsumoto, Takanori Fujiwara, Mitsuaki Goto and Takeshi Endo

      Article first published online: 19 MAY 2015 | DOI: 10.1002/pola.27682

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      Polycarbosilanes having glucose or glucosamine-derived structures in the polymer side chains were synthesized via ene-thiol reaction of polycarbosilane having C=C double bonds with thiol-modified glucose or thiol-modified glucosamine. Their application to materials for cell cultivation was investigated.

    2. RAFT polymerization in supercritical carbon dioxide based on an induced precipitation approach: Synthesis of 2-ethoxyethyl methacrylate/acrylamide block copolymers

      Gerard Hawkins, Per B. Zetterlund and Fawaz Aldabbagh

      Article first published online: 13 MAY 2015 | DOI: 10.1002/pola.27688

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      A new controlled/living heterogeneous polymerization technique in benign supercritical CO2 is described involving the formation of monomer-swollen seed particles by precipitation of MacroRAFT agent prior to polymerization. The technique offers the large scale synthesis of poly(2-ethoxyethyl methacrylate)-b-poly(acrylamides) useful for biomedical applications, which can be isolated as powders at high conversion circumventing the requirement for volatile organic solvents.

    3. Synthesis of pyrene-capped polystyrene by free radical polymerization and its application in direct exfoliation of graphite into graphene nanosheets

      Haining Wang, Zhao Chen, Lanxia Xin, Jian Cui, Shuai Zhao and Yehai Yan

      Article first published online: 7 MAY 2015 | DOI: 10.1002/pola.27675

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      By use of a particularly designed azo-based pyrenyl compound as the initiator, free radical polymerization was demonstrated to be a feasible technique for synthesis of single pyrene group end-capped polystyrene, which could be applied as an efficient dispersant in direct exfoliation of graphite into graphene nanosheets.

    4. Oxetane-terminated telechelic epoxy-functional polyesters as cationically polymerizable thermoset resins: Tuning the reactivity with structural design

      Susana Torron and Mats Johansson

      Article first published online: 7 MAY 2015 | DOI: 10.1002/pola.27673

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      Telechelic oligomers containing oxetane end groups and epoxides in the main chain have been prepared through enzyme catalyzed esterification of a biobased monomer. Control of the final mechanical properties of the networks is achieved by tailoring the reactivity of those groups. The formed oligomers revealed a preferred copolymerization route to build the thermosets when compared with the homopolymerizations.

    5. Synthesis and phase behavior of a polynorbornene-based molecular brush with dual “jacketing” effects

      Yangyang Qiao, Jing Ping, Haijian Tian, Qikai Zhang, Sheng Zhou, Zhihao Shen, Shijun Zheng and Xinghe Fan

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27646

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      A series of molecular brushes with dual “jacketing” effects were synthesized by ATRP and ROMP using the “grafting through” method. All the PNb-g-PMPCS molecular brushes form a ΦN phase. The confinement effect and the increased MW effect of the brush architecture play important roles in the phase behaviors of these molecular brushes.

    6. Consideration on formation mechanism of aromatic polyamide hollow spheres prepared by reaction-Induced phase separation

      Hirofumi Nakayama, Yuji Fujitsu, Tetsuya Uchida, Shinichi Yamazaki and Kunio Kimura

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27683

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      Formation mechanism of poly(1,4-phenylene-5-hydroxyisophthalamide) hollow spheres prepared by the reaction-induced phase separation during polymerization was considered from the view points of eliminated small molecules, polymer structure, and cross-linking reaction. Water was the most desirable to form gas-bubbles and rigid polymer structure was also needed for the rapid solidification of droplets. Further, the formation of the cross-linked skin layer was important to encapsulate gas-bubbles in the droplets.

    7. Fabrication and characterization of UV-crosslinkable thermoresponsive composite fibers with magnetic properties

      Shih-Ru Huang, King-Fu Lin, Trong-Ming Don, Wen-Yen Chiu and Mei-Fei Lin

      Article first published online: 6 MAY 2015 | DOI: 10.1002/pola.27684

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      Stimuli-responsive materials recently received much attention due to their unique sensitivities and functionalities. In order to manufacture functional drug carrier with higher drug loading, electrospinning technique was used to fabricate fibrous composite with thermoresponsivity and magnetic properties. Drug release behavior of magnetic thermoresponsive composite (MTC) drug carrier was studied in the article. It has potential in controlled drug release system.

    8. RAFT of sulfobetaine for modifying poly(glycidyl methacrylate) microspheres to reduce nonspecific protein adsorption

      Jana Koubková, Hana Macková, Vladimír Proks, Miroslava Trchová, Jiří Brus and Daniel Horák

      Article first published online: 30 APR 2015 | DOI: 10.1002/pola.27681

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      Monodisperse poly(glycidyl methacrylate) microspheres were grafted with zwitterionicpoly{[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonimum hydroxide} using RAFT polymerization initiated from the particle surface. Increasing amounts of polysulfobetaine on the surface rendered the microspheres hydrophilic and biocompatible and significantly reduced nonspecific adsorption of bovine serum albumin.

    9. Bioreducible hyperbranched polyglycerols with disulfide linkages: Synthesis and biocompatibility evaluation

      Rajesh A. Shenoi, Irina Chafeeva, Benjamin F. L. Lai, Sonja Horte and Jayachandran N. Kizhakkedathu

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27672

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      Anionic ring opening polymerization of glycidol and a disulfide-containing epoxide monomer was used for the synthesis of multifunctional and water-soluble disulfide-bearing biodegradable hyperbranched polyglycerols both in the low and high molecular weight range. The polymers were degraded to lower molecular weight polymer fragments in presence of reducing agents such as TCEP, DTT, and glutathione. The polymers also showed excellent biocompatibility profiles even at very high concentrations and could be useful as nanocarriers for intracellular delivery of therapeutics.

    10. Shape memory biomaterials prepared from polyurethane/ureas containing sulfated glucose

      Qinyuan Chai, Yongshun Huang and Neil Ayres

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27668

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      Crosslinked polymers were synthesized using monomers modified with glucose. The polymers showed shape memory behavior. A glass transition temperature of 39 °C, close to physiological temperatures, was obtained. The polymer recovered to the permanent shape when heated to 50 °C. The surface of a film of the polymer can be sulfated to achieve increased blood-compatibility without sacrificing the shape memory properties.

    11. Preparation of microporous polymers in the form of particles and a thin film from hyperbranched polyphenylenes

      Min Chul Cha, Yoonbin Lim and Ji Young Chang

      Article first published online: 29 APR 2015 | DOI: 10.1002/pola.27670

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      A hyperbranched polyphenylene with numerous unreacted bromophenyl end groups was used as a multifunctional building block for the synthesis of a microporous organic polymer. The precursor polymer could be shaped into a film and the subsequent cross-linking reaction produced an insoluble porous film.

  18. Rapid Communication

    1. Facile and versatile platform for the preparation of functional polyethylenes via thiol-ene chemistry

      Zeyun Xiao, Christopher W. Bennett and Luke A. Connal

      Article first published online: 27 APR 2015 | DOI: 10.1002/pola.27667

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      A modular approach to the preparation of functional polyethylenes is presented. Polycyclooctene polymers are prepared via ring opening metathesis polymerization. The internal alkene bonds of the subsequent polyclycooctenes are exploited using photochemical thiol–ene click chemistry. A range of branched, amphiphilic, and fluorinated polyethylenes are synthesized.

  19. Articles

    1. Antibacterial poly(ethylene terephthalate) surfaces obtained from thymyl methacrylate polymerization

      Sophie Bedel, Bénédicte Lepoittevin, Ludovic Costa, Olivier Leroy, Diana Dragoe, Jérôme Bruzaud, Jean-Marie Herry, Morgan Guilbaud, Marie-Noëlle Bellon-Fontaine and Philippe Roger

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27647

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      A method for fabrication of poly(thymyl methacrylate) brushes grafted on poly(ethylene terephthalate) films is described. The monomer is obtained from thymol essential oil. The modified surfaces are prepared by “grafting from” using atom transfer radical polymerization and present antibacterial properties against different bacteria strains.

    2. Oligomeric aliphatic–aromatic ether containing phthalonitrile resins

      Matthew Laskoski, Arianna Neal, Mollie B. Schear, Teddy M. Keller, Holly L. Ricks-Laskoski and Andrew P. Saab

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27659

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      A series of aliphatic containing phthalonitrile resins have been synthesized and characterized. The cured polymer shows good physical properties and low water absorption.

    3. Energy transfer through heterogeneous dyes-substituted fluorene-containing alternating copolymers and their dual-emission properties in the films

      Hyeonuk Yeo, Kazuo Tanaka and Yoshiki Chujo

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27652

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      A series of the alternating fluorene copolymers modified with pyrene or 9,10-diphenylanthracene and BODIPY at the cardo carbon based on the red-emissive donor-acceptor structure were prepared. From the measurements of the optical properties, the energy transfer efficiencies were evaluated. In summary, variable energy transfer efficiencies were observed between the side chains and from the side chain to the main chain. Finally, the dual-emissive polymers were obtained in the film states.

    4. Synthesis and characterization of chiral poly(alkyl isocyanates) by coordination polymerization using a chiral half-titanocene complex

      Ioannis Choinopoulos, Spyros Koinis and Marinos Pitsikalis

      Article first published online: 23 APR 2015 | DOI: 10.1002/pola.27669

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      Chiral polymers are used in high technology applications. The chirality of polyisocyanates derives from their helical structure. The chiral 2-(S)-butoxy group of the novel half-titanocene complex [CpTiCl2(O-(S)−2-Bu)] is responsible for the production of the left-handed poly(alkyl isocyanate) helices exclucively. The polymerization reaction is well controlled and proceeds in a chiral manner. The polymers maintain their structure in a wide range of temperatures. Cyclotrimerization, instead of polymerization is favored for the sterically hindered monomers.

    5. Synthesis and structure–property relationship of carbazole-alt-benzothiadiazole copolymers

      Jules Oriou, Feifei Ng, Georges Hadziioannou, Cyril Brochon and Eric Cloutet

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27660

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      Four π-conjugated copolymers based on carbazole and benzothiadiazole (PCBT) were prepared by Suzuki cross-coupling reaction. Their structures differed by linkage position and geometry of the solubilizing chain on the carbazole subunits. These organic materials were characterized and showed promising properties for organic electronics applications. The differences in structure were shown to influence the optical properties.

    6. Hyperbranched polytriazine grafted reduced graphene oxide and its application

      Chao Liu, Hongxia Yan, Lingxia Yuan, Zhengyan Chen and Mengmeng Zhang

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27661

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      Hyperbranched polytriazineis used to modify reduced graphene oxide, making it amphipathic and improving its distribution in polymer composites. In turn, this greatly improves the thermal stability and electrical conductivity of its polymer composites as compared with unmodified graphene oxide composites.

    7. Understanding of nanogels swelling behavior through a deep insight into their morphology

      Aintzane Pikabea, Garbiñe Aguirre, Jose I. Miranda, Jose Ramos and Jacqueline Forcada

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27653

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      The morphology and swelling behavior of biocompatible and dual-stimuli-responsive nanogels crosslinked with different crosslinkers were analyzed and related by combining the Flory–Rehner theory with 1H-NMR and PCS data.

    8. A benign initiating system for cationic polymerization of isobutyl vinyl ether: Silver salt/aryl(alkyl) halide/lewis base

      Li Lin, Guangyou Zhang, Koichi Kodama, Mikio Yasutake and Takuji Hirose

      Article first published online: 18 APR 2015 | DOI: 10.1002/pola.27656

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      Aryl(alkyl) halides and silver salts were studied as an ecofriendly initiating system for cationic polymerization of isobutyl vinyl ether (IBVE). Me2S was shown to be an effective Lewis base (LB) for controlling the reaction. Detailed study of various benzyl cations and the order of reagent addition showed that the reaction was controlled by the steric and electronic features of the benzyl halides, LBs, and IBVE. A plausible reaction mechanism was proposed.

    9. A new route to atactic polypropylene: The second life of premetallocene homogeneous polymerization catalyst

      Yury V. Kissin, Laura A. Rishina, Svetlana S. Lalayan and Vadim G. Krasheninnikov

      Article first published online: 17 APR 2015 | DOI: 10.1002/pola.27651

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      Ternary Ti(Oiso-Pr)4 - AlEt2Cl/MgBu2 catalyst polymerizes propylene at 30–50 °С to a predominantly amorphous atactic polymer. The 13C NMR spectrum of the heptane-soluble fraction of the polymer consists of signals of various stereo-irregular pentads and heptads; its [mmmm] = 0.21.

    10. Lysine-based functional blocked isocyanates for the preparation of polyurethanes provided with pendant side groups

      Jie Yin, Jur Wildeman and Ton Loontjens

      Article first published online: 15 APR 2015 | DOI: 10.1002/pola.27658

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      A general methodology was found to prepare linear polyurethanes, decorated with pendant (bio)functional side groups by using (bio)functionalized blocked diisocyanates and polyols. The functionalizable blocked isocyanate precursor, caprolactam blocked lysine diisocyanate methyl ester, was prepared in high yields by reacting the methyl ester of lysine with carbonyl biscaprolactam.

    11. Polyaniline copolymers with solvent-mimic side chains

      Seung-Chul Lee, Chan-Keun Jung, Hoon-Joo Jung, Suck-Hyun Lee and O-Pil Kwon

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27648

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      New polyaniline copolymers with solvent-mimic side chains for enhanced processability in various solvents were investigated. The solvent-mimic side chains, benzyloxypropyl (BOP) and dihydroxypropoxy (DHP), were introduced into copolymers and used with nonpolar aromatic and polar alcoholic solvents, respectively. Polyaniline copolymers with a small amount of side chains (<2 mol %) exhibit higher electric conductivity and better film-forming ability in nonpolar aromatic solvent than polyaniline homopolymer.

    12. Demonstration of isospecific free radical polymerization of acrylate controlled by conformation and chirality of monomer

      Hitoshi Tanaka, Yoshitaka Matsubara, Katsuhiko Kusunoki, Naoki Saito and Tatsuya Kibayashi

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27649

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      A high isotactic heat-resistant functional polymer was prepared through a stereospecific free radical polymerization of bio-based acrylate derived from lactic acid. The work demonstrates the importance of chirality and conformation of monomer in the stereospecific polymerization, giving a clue to understanding stereochemistry in free radical polymerization and constructing a tailor-made polymer. A new approach to a sustainable synthesis of polymers in mild conditions is also established.

    13. Facile fabrication of fast recyclable and multiple self-healing epoxy materials through diels-alder adduct cross-linker

      Xiao Kuang, Guoming Liu, Xia Dong, Xianggui Liu, Jianjun Xu and Dujin Wang

      Article first published online: 11 APR 2015 | DOI: 10.1002/pola.27655

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      A reversibly cross-linked epoxy resin with efficient reprocessing and intrinsic self-healing has been prepared from a newly synthesized diamine Diels-Alder (DA) adduct cross-linker and a commercial epoxy oligomer. The methodology developed in this work takes smart and environmentally benign epoxy to the next level of simplicity and provides new insights in the modification of traditional engineering plastics as a functional material.

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