Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 6

15 March 2010

Volume 48, Issue 6

Pages 1251–1460

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      Chemistry of 2-oxazolines: A crossing of cationic ring-opening polymerization and enzymatic ring-opening polyaddition (pages 1251–1270)

      Akira Makino and Shiro Kobayashi

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23906

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      Cationic ring-opening polymerization (CROP) of 2-oxazoline monomers produces poly(N-acylethylenimine)s. Enzymatic ring-opening polyadditon (EROPA) of sugar 2-oxazoline monomers gives amino-polysaccharides. Despite involving chemistry of 2-oxazolines, these reactions look quite different, yet they merged into polymer synthesis field. The key for the polymerizations to occur is an appropriate combination of a catalyst and a designed monomer. From the mode of reaction, an acid-catalyzed cationic ring-opening polyaddition (ROPA) is considered as a crossing where CROP and EROPA meet. The present article describes recent advancements of the polymerizations involving these 2-oxazoline chemistries.

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    1. Chemically amplified photoresists for 193-nm photolithography: Effect of molecular structure and photonic parameters on photopatterning (pages 1271–1277)

      Hassan Ridaoui, Ali Dirani, Olivier Soppera, Esma Ismailova, Cyril Brochon, Guy Schlatter, Georges Hadziioannou, Raluca Tiron, Philippe Bandelier and Claire Sourd

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23866

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      Among other resist platforms, Chemically Amplified Photoresists (CAR) are widely used because of their excellent properties in terms of resolution, sensitivity and etching resistance. CAR with wellcontrolled polymer structures were prepared and investigated. In particular, the impact of the polymer structure on the lithographic performance was evaluated. Linear and branched polymers with various molecular weight and polydispersity were compared. We focused on the dependency of the photosensitivity of the resist with the structural parameters. These results allow further understanding of the fundamental phenomena involved by 193 nm irradiation.

    2. Metal-free synthesis of responsive polymers: Cloud point tuning by controlled “click” reaction (pages 1278–1286)

      C. Remzi Becer, Kenta Kokado, Christine Weber, Aydin Can, Yoshiki Chujo and Ulrich S. Schubert

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23872

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      Advances in controlled radical polymerization techniques allow synthesizing functional polymers with clickable groups. A series of random copolymers of pentafluorostyrene and oligo(ethyleneglycol) methacrylate or dimethyl(aminoethyl) methacrylate have been synthesized using nitroxide-mediated polymerization. These copolymers exhibit varying lower critical solution temperatures in water at different comonomer ratios. Moreover, the cloud points of thermoresponsive copolymers could be tuned further by reacting with thiophenol that reacts rapidly with pentafluorophenyl groups at room temperature. Both polymerization and click reaction were used in the absence of any metal catalyst.

    3. Sol-gel transition behavior of amphiphilic comb-like poly[(PEG-b-PLGA)acrylate] block copolymers (pages 1287–1297)

      Chung Won Park and Sung Chul Kim

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23877

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      Comb-like poly((poly(ethylene glycol)-b-(poly(lactic acid-co-glycolic acid))acrylate-co-acrylic acid) (poly((PEG-b-PLGA)A-co-AA)) copolymers were synthesize, and the effects of comb-like amphiphilic block copolymer architectures on the physical properties such as sol-gel transition and micellization behaviors with the change of temperature and pH were examined.

    4. Synthesis and characterization of donor–bridge–acceptor alternating copolymers containing perylene diimide units and their application to photovoltaic cells (pages 1298–1309)

      Mao-Chuan Yuan, Ming-Hsin Su, Mao-Yuan Chiu and Kung-Hwa Wei

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23889

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      The properties of alternating copolymers featuring coplanar cyclopentadithiophene and good hole-transporting carbazole units conjugated in the main chain and electron-deficient perylene diimide moieties (large molar absorption coefficient) incorporated into the side chains have been studied; the characteristics of photovoltaic cells incorporating these copolymers were also investigated.

    5. Triphenylamine-based fluorescent conjugated copolymers with pendant terpyridyl ligands as chemosensors for metal ions (pages 1310–1316)

      Yi Cui, Qi Chen, Dan-Dan Zhang, Jie Cao and Bao-Hang Han

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23890

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      Two well-defined triphenylamine-based fluorescent conjugated copolymers with pendant terpyridyl ligands were successfully designed and synthesized by Suzuki coupling polymerization. It is found that the terpyridine-bearing poly(triphenylamine-alt-fluorene) polymer shows a much higher sensitivity to Fe3+ ion, as compared with the analogous polymer poly(triphenylamine-alt-N-ethylcarbazole). It demonstrates that the polymers with a same receptor may show different sensitivity to analytes owing to their different structure in the main backbone.

    6. Low-CTE photosensitive polyimide based on semialicyclic poly(amic acid) and photobase generator (pages 1317–1323)

      Tomohito Ogura, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23892

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      A negative-type photosensitive polyimide (PSPI) based on semialicyclic poly(amic acid) (PAA) and {[(4,5-dimethoxy-2-nitrobenzyl)oxy]carbonyl} 2,6-dimethylpiperidine (DNCDP) as a photobase generator has been developed as a next-generation buffer coat material. This PSPI was directly formed from the PAA polymerization solution and showed a low coefficient of thermal expansion of 16 ppm/K.

    7. Synthesis and properties of crosslinked chiral nanoparticles via RAFT miniemulsion polymerization (pages 1324–1331)

      Wenliang Xu, Zhenping Cheng, Lifen Zhang, Zhengbiao Zhang, Jian Zhu, Nianchen Zhou and Xiulin Zhu

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23893

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      Crosslinked chiral nanoparticles were successfully synthesized via RAFT miniemulsion polymerization of 6-O-p-vinylbenzyl-1,2:3,4-Di-O-isopropylidene-D-galactopyranose (VBPG) using linear poly(VBPG) as the macro-RAFT agent. The effect of the amount of crosslinker divinylbenzene (DVB) on the nanoparticle size and chiral separation properties of the obtained nanoparticles were investigated in detail using four racemates ±-3-Amino-1,2-propanediol, D,L-arabinose, D,L-tartaric acid, and D,L-mandelic acid.

    8. A facile method for the preparation of monodisperse hollow silica spheres with controlled shell thickness (pages 1332–1338)

      Shunsheng Cao, Xin Jin, Xinhua Yuan, Weiwei Wu, Jie Hu and Weichen Sheng

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23894

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      Fabrication of hollow structures by templating against hard particles conventional involves multi-steps process. In this article, a facile method for the preparation of the monodisperse hollow silica spheres (see SEM image) was reported by using cationic polystyrene as templates. Silica encapsulation and dissolution of the PS core can be done in situ by modification of the reaction conditions. Subsequently, FT-IR, TEM, SEM, TGA, and BET experiments revealed that the well-defined hollow silica spheres could be obtained by this facile process.

    9. Chemical synthesis and characterization of poly(aniline-co-ethyl 3-aminobenzoate) copolymers (pages 1339–1347)

      Marija R. Gizdavic-Nikolaidis, Zoran D. Zujovic, Sudip Ray, Allan J. Easteal and Graham A. Bowmaker

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23895

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      Poly(aniline-co-ethyl 3-aminobenzoate) (3EABPANI) copolymers and homopolymer poly(ethyl 3-aminobenzoate) (P3EAB) were chemically synthesized using potassium iodate as an oxidizing agent. The 3EABPANI copolymers show two features, one amorphous and the other a crystalline domain, which may be associated with the different reactivities of the aniline and ethyl 3-aminobenzoate (3EAB) monomers. P3EAB displays crystalline morphology with particles with well-defined edges and lamellar structure. The crystalline morphology in P3EAB may result from intramolecularly hydrogen-bonded 3EAB units.

    10. Room-temperature RAFT copolymerization of 2-chloroallyl azide with methyl acrylate and versatile applications of the azide copolymers (pages 1348–1356)

      Guang Li, Hu Wang, Haiting Zheng and Ruke Bai

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23896

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      A new vinyl azide monomer, 2-chlorallyl azide (CAA), synthesized from a commercially available reagent, was successfully copolymerized with methyl acrylate (MA) via room temperature RAFT polymerization. Fluorinated block azide copolymer and graft copolymers were synthesized through the chain extension RAFT polymerization and “click” reaction, respectively. Moreover, the hydrophilic property of the glass sheet was modified successfully with different azide copolymers based on the crosslinking reaction upon UV irradiation at ambient temperature.

    11. Chain-growth condensation polymerization of 4-aminobenzoic acid esters bearing tri(ethylene glycol) side chain with lithium amide base (pages 1357–1363)

      Kazuo Yoshino, Kotaro Hachiman, Akihiro Yokoyama and Tsutomu Yokozawa

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23897

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      For synthesis of well-defined poly(p-benzamide) bearing hydrophilic side chains, polymerization of p-aminobenzoic acid ester 1 having a tri(ethylene glycol) side chain was investigated. Polymerization of the phenyl ester monomer 1b with lithium 1,1,1,3,3,3-hexamethyldisilazide (LiHMDS) at −20 °C gave the objective poly1b with controlled molecular weight and narrow molecular weight distribution. Furthermore, block copolymers of poly1b having the hydrophilic side chains and poly(N-octyl-4-benzamide) having hydrophobic side chains were synthesized in one pot. When a THF solution of poly1b was allowed to dry on a glass plate, spherical aggregates were formed.

    12. ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers (pages 1364–1373)

      Temel Ozturk, Sevil Savaskan Yilmaz, Baki Hazer and Yusuf Z. Menceloglu

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23898

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      A combination of ATRP and fee radical polymerization was used in the synthesis of block and graft copolymers using peroxygen-containing poly-MMA as a macroinitiator which was prepared from the ATRP of MMA in the presence of bis(4,4′-bromomethyl benzoyl peroxide). The peroxygen groups do not decompose during the ATRP because low reaction temperatures used for the ATRP are not enough to decompose them. Poly)MMA-b-S) block and crosslinked poly)MMA-g-PBd) and poly)MMA-g-RSS-3) graft copolymers have been prepared by using these macroperoxy initiators. Generally ATRP are carried out at high temperatures. We have reported ATRP is particularly effective in the bulk under low temperatures.

    13. Phosphido-diphosphine pincer group 3 complexes as efficient initiators for lactide polymerization (pages 1374–1382)

      Mina Mazzeo, Marina Lamberti, Ilaria D'Auria, Stefano Milione, Jonas C. Peters and Claudio Pellecchia

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23899

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      New yttrium and scandium bis-alkyl complexes supported by phosphido pincer ligands have been synthesized and tested in ring opening polymerization of lactide. They showed high catalytic activities and a good molar-mass control indicative of a “single site” nature of the catalyst. Interestingly, yttrium complexes were also able to initiate the ROP of lactide in absence of solvent.

    14. Chirality sensing of chiral pyrrolidines and piperazines with a liquid crystalline dynamic helical poly(phenylacetylene) bearing ethyl phosphonate pendant groups (pages 1383–1390)

      Masao Morimoto, Kazumi Tamura, Kanji Nagai and Eiji Yashima

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23900

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      A liquid crystalline, dynamic helical poly(phenylacetylene) bearing ethyl phosphonate pendants was sensitive to the chirality of pharmaceutically important chiral pyrrolidines and piperazines in DMSO and water, thus showing a characteristic induced circular dichroism in the UV-vis region of the polymer backbone. The polymer formed a lyotropic liquid crystalline phase in concentrated water solutions, resulting in nematic phase, which changed to cholesteric counterpart in the presence of chiral amines.

    15. Effect of pH and generation of dendron on single-step synthesis of gold nanoparticles using PEGylated polyamidoamine dendron in aqueous medium (pages 1391–1398)

      Atsushi Harada, Akihiko Yuzawa, Takeshi Kato, Chie Kojima and Kenji Kono

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23901

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      PEGylated polyamidoamine (PAMAM) dendrons were synthesized through PEGylation of primary amines at the periphery of second, third, and fourth generation dendrons. Change in surface plasmon resonance for the mixture of Au(III) precursors and PEGylated PAMAM dendrons was dependent on pH in aqueous medium, demonstrating the importance of the balance between protonated and deprotonated tertiary amines and the reactivity of Au(III) precursors. By using PEGylated PAMAM dendrons with hemisphere shape, the obtained Au NPs had narrow size distribution with small average size because of the limitation of intermolecular space among PEGylated PAMAM dendrons for the growth to gold nanoparticles.

    16. A simple methodology for the synthesis of heterotelechelic protein–polymer–biomolecule conjugates (pages 1399–1405)

      Jingquan Liu, Huiyun Liu, Volga Bulmus, Lei Tao, Cyrille Boyer and Thomas P. Davis

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23902

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      A chain transfer agent (CTA) was functionalized with α,ω-pyridyl disulfide (PDS) groups. Subsequently, one of the PDS groups was covalently attached to bovine serum albumin (BSA) at the specific free thiol group on the cysteine residue through a disulfide linkage. The second PDS group remained intact, as it was found to be inaccessible to further BSA functionalization. The BSA-macro-RAFT agent was then used to prepare BSA-polymer conjugates via in situ polymerization at ambient temperature. After polymerization, the remaining terminal PDS groups were then utilized to covalently attach free thiol tethered precursors to afford hetero-biofunctional conjugates.

    17. Preparation and properties of oxadiazole-containing polyacetylenes as electron transport materials (pages 1406–1414)

      Xin Wang, Shanyi Guan, Hongyao Xu, Xinyan Su, Xuhui Zhu and Chun Li

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23904

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      The functional polyacetylene with well electron affinity and high thermal properties prepared by incorporating oxadiazole into polyacetylene effectively enhances external quantum efficiency and the brightness of device, and decreases turn-on voltages of devices when was applied as a ETM in bilayer LEDs.

    18. Synthesis and self-assembly of rod-coil molecules with n-shaped rod building block (pages 1415–1422)

      Ke-Li Zhong, Zhegang Huang, Zhijin Man, Long Yi Jin, Bingzhu Yin and Myongsoo Lee

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23909

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      Rod-coil molecules with n-shaped rod building block were successfully synthesized. In the melt state, molecule with a methoxy group at 10 position of anthracene self-assembles into hexagonal columnar structure, Whereas molecule with an octanyl group at 10 position of anthracene self-organizes into rectangular columnar structure. Further increasing the length of alkyl chain suppresses a liquid crystalline phase and exhibits only a lamellar structure in the solid state. In aqueous medium, these molecules can self-assemble into elongated nanofiber structure with a radial aggregation of aromatic segments.

    19. Synthesis and characterization of cyclopentadithiophene-based low bandgap copolymers containing electron-deficient benzoselenadiazole derivatives for photovoltaic devices (pages 1423–1432)

      In Hwan Jung, Hoyeon Kim, Moo-Jin Park, Bongjun Kim, Jong-Hwa Park, Eunjae Jeong, Han Young Woo, Seunghyup Yoo and Hong-Ku Shim

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23910

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      We have synthesized CDT-based copolymers containing the electron-withdrawing benzoselenadiazole moieties. Both PCBSe and PCT2BSe exhibited exceedingly low optical bandgaps of 1.37–1.46 eV, which are ideal for the absorption of a large fraction of solar spectrum. PCT2BSe showed better photovoltaic characteristics than did PCBSe, because the absorption band of the PCT2BSe/PCBM blend was larger than that of PCBSe/PCBM. When the polymers were blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), PCT2BSe showed the best performance, with an open circuit voltage of 0.55 V, a short-circuit current of 6.63 mA/cm2, and a power conversion efficiency of 1.34% under AM 1.5 G.

    20. Flexible nanocrystalline-titania/polyimide hybrids with high refractive index and excellent thermal dimensional stability (pages 1433–1440)

      Guey-Sheng Liou, Po-Han Lin, Hung-Ju Yen, Yang-Yen Yu and Wen-Chang Chen

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23914

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      Novel flexible and high titania content PI–TiO2 hybrid optical films could be successfully prepared from newly soluble hydroxyl-substituted polyimides. These novel flexible hybrid films revealed excellent thermal dimensional stability, tunable refractive index, and potential optical applications.

    21. A novel type of optically active helical polymers: Synthesis and characterization of poly(α,β-unsaturated ketone) (pages 1441–1448)

      Shi Wu, Nianfa Yang, Liwen Yang, Jing Cao and Ji Liu

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23915

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      New α,β-unsaturated ketone monomers, MVK, and MBEK, were synthesized and anionically polymerized. Poly-MVK had a tremendous optical rotation and the study on the CD of poly-MVK and relative compounds confirmed that poly-MVK kept helical conformation in solution. This conclusion was also confirmed by the fact that the CD signal intensity of poly-MBEK were not enough large due to backbone flexibility caused by the effective isolation of the backbone from the bulky menthyl. The excess value of one-handed helicity of poly-MVK decreased with the increase of polymerization temperature.

    22. Living cationic polymerization of an azide-containing vinyl ether toward addressable functionalization of polymers (pages 1449–1455)

      Shohei Ida, Makoto Ouchi and Mitsuo Sawamoto

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23916

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      We first achieved a living cationic polymerization of azide-containing monomer, 2-azidoethyl vinyl ether (AzVE), with SnCl4 as an activator. The molecular weights of the produced polymers were directly increased as the conversion, and the molecular weight distributions were narrow (Mw/Mn ∼ 1.2). The high controllability was proved by successful block copolymerization with 2-chloroethyl vinyl ether (CEVE). We also demonstrated quantitative functionalization of the side group via Staudinger reduction or copper-catalyzed azide-alkyne 1,3-cycloaddition (CuAAC) under very mild condition. Thus, this system should be very fundamental to construction of functional vinyl ether-based polymers with well-defined structures.

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      Synthesis and characterization of dialkoxy substituted poly(phenylenevinylene) benzobisoxazoles (pages 1456–1460)

      Jared F. Mike, Andrew J. Makowski, Timothy C. Mauldin and Malika Jeffries-El

      Version of Record online: 3 FEB 2010 | DOI: 10.1002/pola.23869

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      A new route for the synthesis of soluble, alkoxy-substituted poly(p-phenylenevinylene) benzobisoxazoles has been developed. The target polymers can be prepared in three steps: the Lewis acid catalyzed condensation of corresponding diamino benzene diols with triethyl orthochloroacetate, the Arbuzov reaction of the resultant benzobisoxazole, and the Horner-Wadsworth-Emmons polymerization of 2,5-didodecyloxyterephthalaldehyde and the resulting 2,6-dimethylbenzobisoxazole-diethylphosphonate esters.

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