Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 3

1 February 2007

Volume 45, Issue 3

Pages 333–552

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      Novel polymers based on atom transfer radical polymerization of 2-methoxyethyl acrylate (pages 333–340)

      Melania Bednarek, Katja Jankova and Søren Hvilsted

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21784

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      A new monomer 2-methoxyethyl acrylate (MEA) has been employed in ATRP. The polymerization initiated by ethyl 2-bromoisobutyrate and catalyzed by Cu(I)Br/HMTETA in both bulk and toluene solution proceeds in a controlled manner. The synthesis of this biocompatible polymer, PMEA, as well as of the block copolymers containing PMEA and PMMA blocks was accomplished by ATRP too in order to expand the PMEA material versatility in medical devices. The depicted polymers are characterized by SEC, FTIR, MALDI-TOF MS, 1H NMR, and contact angle (CA) measurements. The differences observed in water CAs of the PMEA, PMMA, and the block copolymers hereof play a decisive role for surface characteristics of films prepared from the block copolymers. [Color figure can be viewed in the online issue, which is available at]

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    1. Synthesis and characterization of diphenylaminodiphenyl stryl based alternating copolymers (pages 341–347)

      Qinghua Zhao, Yun-Hi Kim, Thi Tuyet Mai Dang, Dong-Cheol Shin, Hong You and Soon-Ki Kwon

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21740

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      Poly{4,4′-biphenylene-α-[4″-(N,N′-diphenylamino)diphenyl]vinylene-alt-5-(2′-ethylhexyloxy)-2-methoxybenzene} and poly {4,4′-biphenylene-α-[4″-(N,N′-diphenylamino)diphenyl]vinylene-alt-9, 9-dihexylfluorene} had a regular structure of alternation between diphenylaminobiphenylated stryl and dihexylfluorene moieties or between diphenylaminobiphenylated stryl and 5-(2′-ethylhexyloxy)-2-methoxybenzene moieties. The indium tin oxide/poly(3,4-ethylene dioxythiophene)/polymer/LiF/Al devices with poly{4,4′-biphenylene-α-[4″-(N,N′-diphenylamino)diphenyl]vinylene-alt-5-(2′-ethylhexyloxy)-2-methoxybenzene} or poly{4,4′-biphenylene-α-[4″-(N,N′-diphenylamino) diphenyl]vinylene-alt-9,9-dihexylfluorene} as the emitting layer showed blue emissions (maximum wavelength = 460 or 487 nm) with maximum brightness of 250 or 1000 cd/m2, respectively.

    2. Influence of a reversible addition–fragmentation chain transfer agent in the dispersion polymerization of styrene (pages 348–360)

      Prakash J. Saikia, Jung Min Lee, Byung H. Lee and Soonja Choe

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21834

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      Dispersion polymerization was applied to the controlled/living free-radical polymerization of styrene with a reversible addition–fragmentation chain transfer polymerization (RAFT) agent in the presence of poly(N-vinylpyrrolidone) and 2,2′-azobisisobutyronitrile in an ethanol medium. The effects of the polymerization temperature and the postaddition of RAFT on the polymerization kinetics, molecular weight, polydispersity index, particle size, and particle size distribution were investigated and found to be strongly dependent on both the temperature and postaddition of RAFT.

    3. ABA triblock copolymers with a ring-opening metathesis polymerization/macromolecular chain-transfer agent approach (pages 361–373)

      Karen A. Switek, Kwanho Chang, Frank S. Bates and Marc A. Hillmyer

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21754

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      ABA triblock copolymers containing polystyrene (A) and polycyclooctene (B) were synthesized with a ring-opening metathesis polymerization/chain-transfer approach. Polystyrene, containing appropriately placed olefins, was prepared by anionic polymerization and served as a macromolecular chain-transfer agent for the ring-opening metathesis polymerization of cyclooctene. These unsaturated polymers were subsequently converted to the corresponding saturated triblock copolymers of polycyclohexylethylene (A) and polyethylene (B) with a simple heterogeneous catalytic hydrogenation step.

    4. Kinetic analysis of the cross reaction between dithioester and alkoxyamine by a Monte Carlo simulation (pages 374–387)

      Yong Ao, Junpo He, Xueqin Han, Yang Liu, Xiaojun Wang, Deqin Fan, Jiangtao Xu and Yuliang Yang

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21798

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      A model reaction between dithioester and alkoxyamine is proposed to investigate the mechanism and kinetics of the reversible addition–fragmentation chain transfer process, in which alkoxyamine plays the role of the radical source. With a Monte Carlo simulation, the kinetics of the model reaction is analyzed. Although pure alkoxyamine obeys the law of the persistent radical effect, the presence of dithioester results in different kinetic behaviors, which depend on the rate constants of addition and fragmentation reactions. The effect of cross termination between the intermediate and alkyl radicals, as well as the possibility of measuring the rate constant of addition with the kinetic model, is also discussed.

    5. Synthesis and characterization of a main-chain-type conjugated copolymer containing rare earth with photocrosslinkable group (pages 388–394)

      Gui-An Wen, Xing-Rong Zhu, Lian-Hui Wang, Jia-Chun Feng, Rui Zhu, Wei Wei, Bo PEng, Qi-Bing Pei and Wei Huang

      Version of Record online: 8 DEC 2006 | DOI: 10.1002/pola.21723

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      A main-chain-type rare earth-containing conjugated polymer, which can be crosslinked photochemically into insoluble film, was prepared by suzuki polycondensation and further complexation with rare earth triisopropyloxide and beta-diketone. The optical properties of the resulting conjugated polymer were characterized in solution, film state, and after photocrosslinking.

    6. Synthesis of macromonomers of acrylic acid by telomerization: Application to the synthesis of polystyrene-g-poly(acrylic acid) copolymers (pages 395–415)

      Cyrille Boyer, Gilles Boutevin, Jean-Jacques Robin and Bernard Boutevin

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21800

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      The synthesis of macromonomers of acrylic acid was performed by telomerization in a three-step process. The first step was the telomerization of tert-butyl acrylate in the presence of thioglycolic acid. Different molecular weights were obtained with different ratios of the monomer to the transfer agent. Good control of the molecular weights and architectures of the oligomers (e.g., the presence of an acid function on the chain end) was observed. The transfer constant of tert-butyl acrylate with thioglycolic acid was assessed (chain-transfer constant = 0.6). In the second step, the terminal unsaturation of the oligomers was obtained by the reaction of the terminal acid groups with 2-isocyanatoethyl methacrylate to yield the macromonomers of tert-butyl acrylate. In the last step, the tert-butyl acrylate groups were hydrolyzed in the presence of trifluoroacetic acid at room temperature. The macromonomers were copolymerized with styrene to obtain graft copolymers, and the reactivity ratios were evaluated. Finally, the copolymers were characterized with surface electron microscopy and atom force microscopy.

    7. One-pot synthesis of 2-phenyl-2-oxazoline-containing quasi-diblock copoly(2-oxazoline)s under microwave irradiation (pages 416–422)

      Richard Hoogenboom, Hanneke M. L. Thijs, Martin W. M. Fijten, Bart M. van Lankvelt and Ulrich S. Schubert

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21711

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      The microwave-assisted statistical copolymerization of 2-phenyl-2-oxazoline with 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline is discussed in this contribution. Kinetic studies of these statistical copolymerizations as well as reactivity ratio determinations were performed to investigate the monomer distribution in these copoly(2-oxazoline)s, demonstrating the formation of quasi-diblock copolymers. In addition, the synthesis of copolymer series with monomer concentrations ranging from 0 to 100 mol % is described. These copolymer series were characterized with 1H NMR spectroscopy, gas chromatography, and gel permeation chromatography. Moreover, the glass-transition temperatures and solubility of these copolymers were studied, and this revealing better mixing of pMeOx with pPhOx than pEtOx with pPhOx.

    8. N-alkoxy pyridinium ion terminated polystyrenes: A facile route to photoinduced block copolymerization (pages 423–428)

      Yasemin Yüksel Durmaz, Görkem Yilmaz and Yusuf Yağci

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21831

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      Photoactive N-alkoxy 4-phenyl pyridinium and N-alkoxy isoquinolinium ion terminated polystyrenes with hexafluoroantimonate counter anion were prepared and characterized. For this purpose, mono- and dibrominated polystyrenes were prepared by Atom Transfer Radical Polymerization (ATRP). The reaction of these polymers with silver hexafluoroantimonate in the presence of 4-phenylpyridine N-oxide and isoquinoline N-oxide in dichloromethane produced desired polymeric salts with the corresponding functionalities. Irradiation of these photoactive polystyrenes produced alkoxy radicals at chain ends capable of initiating free radical polymerization of methyl methacrylate (MMA).

    9. Ring-opening polymerization of substituted ε-caprolactones with a chiral (salen) AlOiPr complex (pages 429–436)

      Mark R. Ten Breteler, Zhiyuan Zhong, Pieter J. Dijkstra, Anja R. A. Palmans, Joris Peeters and Jan Feijen

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21841

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      The ring-opening polymerization (ROP) of ε-caprolactone (ε-CL), 4-methyl-ε-caprolactone (4-MeCL), and 6-methyl-ε-caprolactone (6-MeCL) with a single-site chiral initiator, R,R′-(salen) aluminum isopropoxide (R,R′-[1]), was investigated. The kinetic data for the ROP of the three monomers at 90° in toluene corresponded to first-order reactions in the monomer and propagation rate constants of kε-CL > k4-MeCLk6-MeCL. A notable stereoselectivity with a preference for the R-enantiomer was observed in the ROP of 6-MeCL with R,R′-[1], whereas for 4-MeCL, no stereoselectivity was found.

    10. Synthesis and polymerization of 5-(N,N-dimethylamino)naphthylacetylene with homogeneous rhodium and palladium complexes (pages 437–446)

      J. Gonzalo Rodríguez and Jose Luis Tejedor

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21706

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      The monomer 5-ethynyl-N,N-dimethylnaphthalen-1-amine (2) was satisfactorily obtained by a heterocoupling reaction between 5-iodo-(N,N-dimethyl)naphthalen-1-amine and 2-methyl-3-butyn-2-ol catalyzed by a palladium–copper system and followed by acetone elimination. Poly(5-ethynyl-N,N-dimethylnaphthalen-1-amine) was isolated by the reaction of 2 in the presence of homogeneous rhodium and palladium complexes. On the basis of the spectroscopic data, the polymer always showed a cis–transoidal, stereoregular structure. Moreover, only with the rhodium catalyst in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain-transfer intermediate in the polymer propagation. The kinetics of the catalyzed reaction were analyzed.

    11. Synthesis of poly(vinyl acetate)-graft-polystyrene by a combination of cobalt-mediated radical polymerization and atom transfer radical polymerization (pages 447–459)

      Hiromu Kaneyoshi and Krzysztof Matyjaszewski

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21840

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      The cobalt-mediated radical polymerization of vinyl acetate and vinyl chloroacetate and subsequent addition of 2,2,6,6-tetramethyl-1-piperidinyloxy afforded a 2,2,6,6-tetramethyl-1-piperidinyloxy-terminated macroinitiator in a well-controlled fashion. Then, poly(vinyl acetate)-graft-polystyrene was prepared through the grafting-from atom transfer radical polymerization of styrene with the macroinitiator poly (vinyl acetate-co-vinyl chloroacetate) in the presence of copper complexes formed with bis(2-pyridylmethyl)octadecylamine or tris(2-pyridylmethyl)amine ligands.

    12. Preparation of poly(styrene-co-acrylonitrile)-grafted multiwalled carbon nanotubes via surface-initiated atom transfer radical polymerization (pages 460–470)

      A. M. Shanmugharaj, J. H. Bae, Rati Ranjan Nayak and Sung Hun Ryu

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21858

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      An atom transfer radical polymerization initiator (2-hydroxyethyl bromoisobutyrate) was introduced onto the surface of multiwalled carbon nanotubes (MWCNTs) through a chemical reaction with carboxyl groups generated on the surface because of an acid treatment. Then, the MWCNT-supported atom transfer radical polymerization initiator was used to initiate the polymerization of monomers to form copolymers of styrene and acrylonitrile. The resulting copolymer-wrapped MWCNTs were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, proton nuclear magnetic resonance, Fourier transform Raman spectroscopy, and near-infrared spectroscopy. The copolymer that was generated during polymerization wrapped the MWCNTs to form a shell structure and made them easily dispersible in an organic solvent such as tetrahydrofuran.

    13. Latices of poly(fluoroalkyl mathacrylate)-b-poly(butyl methacrylate) copolymers prepared via reversible addition–fragmentation chain transfer polymerization (pages 471–484)

      Xiaodong Zhou, Peihong Ni, Zhangqing Yu and Feng Zhang

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21861

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      Poly(fluoroalkyl mathacrylate)-block-poly(butyl methacrylate) (PFAMA-b-PBMA) diblock copolymer latices were successfully synthesized by a two-step process, which included the reversible addition–fragmentation chain transfer (RAFT) mediated bulk polymerization of the first monomer and the macro-RAFT-mediated miniemulsion polymerization of the second monomer. The copolymer latex of PFAMA-b-PBMA showed colloidal stability and a narrow molecular weight distribution.

    14. Functionalized poly(oxanorbornene)-block-copolymers: Preparation via ROMP/click-methodology (pages 485–499)

      Christian Kluger and Wolfgang H. Binder

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21867

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      The synthesis of block copolymers on basis of poly(oxanorbornenes) with functional moieties in their side-chains via a combination of ROMP-methods and 1,3-dipolar-“click”-reactions is described. Block copolymers functionalized with ω-azidoalkyl-moieties or terminal acetylenes in one block were prepared starting from N-substituted-ω-bromoalkyl-oxanorbornenes and alkyl-/perfluoroalkyl-oxanorbornenes (Mn = 25,000 g mol−1) and subsequent nucleophilic exchange-reactions. The 1,3-Azide/alkine/“click” reactions with a variety of terminal alkynes using tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1-benzyl-5-methyl-1H-[1,2,3]triazol-4-ylmethyl)-amine as catalysts furnished the substituted block copolymers in high yields, as proven by NMR spectroscopy. The resulting polymers were investigated via temperature-dependent SAXS-methods, revealing their microphase separated structure as well as their temperature-dependent behavior.

    15. Synthesis of optically active poly(N-propargylsulfamides) with helical conformation (pages 500–508)

      Zhigang Zhang, Jianping Deng, Weiguo Zhao, Jianmin Wang and Wantai Yang

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21869

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      An enantiometic pair of novel chiral N-propargylsulfamide monomer was synthesized and polymerized. The corresponding polymers had higher specific rotations with opposite signs compared with those of the corresponding monomers. They performed intense CD signals and UV–vis absorption peaks at about 415 nm. These results demonstrated that the polymers adopted stable helices in nonpolar solvent even at a temperature as high as 50 °C. Hydrogen bonding should be one of the predominant driving forces for poly(N-propargylsulfamides) to adopt the ordered helical conformations. By copolymerization with another achiral monomer, the polymer's solubility was improved drastically.

    16. Complexes of lysozyme with sodium (sulfamate-carboxylate)isoprene/ethylene oxide double hydrophilic block copolymers (pages 509–520)

      Stergios Pispas

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21871

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      Micellar-like complexes between sodium (sulfamate-carboxylate)isoprene/ethylene oxide double hydrophilic block copolymers (SCIEO) and lysozyme were formed in aqueous solutions, at pH 7, because of electrostatic interactions between the anionic groups of the polyelectrolyte block of the copolymers and the cationic groups of lysozyme. The mass and size of the micellar-like complexes depend on the mixing ratio and the molecular characteristics (molecular weight, composition, and architecture) of the copolymer used.

    17. Nanometer-sized polyradical particles: Organic magnetic dot array formed on a silicon microfabricated substrate (pages 521–530)

      Manabu Tanaka, Shingo Imai, Takashi Tanii, Yoshiteru Numao, Naonobu Shimamoto, Iwao Ohdomari and Hiroyuki Nishide

      Version of Record online: 14 DEC 2006 | DOI: 10.1002/pola.21886

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      A magnetically active, purely organic dot array was formed by the selective deposition of polyradical nanoparticles on array-like-formed pits on a silicon substrate. The nanometer-sized polyradical particles, poly(4-methacryoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), were prepared by the emulsion polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-1-acetoxyl followed by a deprotection reaction and oxidation in air. The size (diameter) and radical spin concentration of the polyradical nanoparticles were tunable between the polymerization and oxidation conditions. Electrochemical studies revealed the redox property of the polyradical nanoparticles. The magnetic response image of the polyradical nanoparticles was obtained by magnetic force microscopy, reflecting their radical spin concentrations. These results suggested a possible approach for the use of organic polyradical nanoparticles as organic magnetic dot arrays.

    18. Stability control of the electrooptic effect with new maleimide copolymers containing photoreactive tricyanopyrrolidene-based chromophores (pages 531–542)

      Sang Kyu Lee, Min Ju Cho, Jung-Il Jin and Dong Hoon Choi

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21887

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      New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene-based chromophore. The 2-(3-cyano-4-(2-{4-[hexyl-(6-hydroxy- hexyl)-amino]-phenyl}-vinyl)-5-oxo-1-{4-[4-(3-oxo-3-phenyl-propenyl)-phenoxy]-butyl}-1,5-dihydro-pyrrol-2-ylidene)-malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully.

    19. Polycondensation of activated L-valine and L-leucine esters with various lewis acids (pages 543–547)

      Tadamasa Nemoto, Daisuke Ando, Kensuke Naka and Yoshiki Chujo

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21895

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      We screened a transition metal or a rare-earth triflate as a Lewis acid for the polycondensation of 4-nitrophenyl L-leucinate and L-valinate in N,N-dimethylformamide solutions at room temperature. In the presence of 5 mol % metal triflates, especially scandium(III) trifluoromethanesulfonate, the polymerizations of both monomers were promoted effectively.

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      Poly(p-phenylene)-type polymer composed of an (R,R)-C2-symmetric chiral recurring unit: Solution behavior, packing structure, and large circular dichroism observed with a film of the polymer (pages 548–552)

      Takakazu Yamamoto, Takayuki Iijima, Yoshiki Ozawa, Koshiro Toriumi, Kenji Kubota and Shintaro Sasaki

      Version of Record online: 15 DEC 2006 | DOI: 10.1002/pola.21856

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      (R,R)-PH2Ph(9,10-OSiBu3) shows a tendency to self-assemble and gives strong circular dichroism in its film. A packing model of the polymer is shown.