Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 August 2002

Volume 40, Issue 16

Pages 2719–2893

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      Discovery of dendrimers and dendritic polymers: A brief historical perspective (pages 2719–2728)

      Donald A. Tomalia and Jean M. J. Fréchet

      Version of Record online: 21 JUN 2002 | DOI: 10.1002/pola.10301

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      A brief historical perspective relating the discovery of dendrimers and other dendritic polymers is presented. Dendritic polymers are recognized as the fourth major class of macromolecular architecture consisting of four subclasses, namely, (1) random hyperbranched, (2) dendrigrafts, (3) dendrons, and (4) dendrimers. The previous literature is reviewed with anecdotal events leading to implications for dendrimers in the emerging science of nanotechnology.

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    1. New synthetic method for aromatic polyketones from bis(arylsilane)s and aromatic dicarboxylic acid chlorides (pages 2729–2735)

      Hisashi Takeuchi, Masa-aki Kakimoto and Yoshio Imai

      Version of Record online: 21 JUN 2002 | DOI: 10.1002/pola.10361

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      A new synthetic method for aromatic polyketones was developed through Friedel–Crafts polycondensation of bis(arylsilane) monomers with aromatic dicarboxylic acid chlorides through aromatic electrophilic ipso substitution in a 1,2-dichloroethane solution in the presence of aluminum chloride.

    2. Polyolefin graft copolymers via living polymerization techniques: Preparation of poly(n-butyl acrylate)-graft-polyethylene through the combination of Pd-mediated living olefin polymerization and atom transfer radical polymerization (pages 2736–2749)

      Sung Chul Hong, Shijun Jia, Mircea Teodorescu, Tomasz Kowalewski, Krzysztof Matyjaszewski, Amy C. Gottfried and Maurice Brookhart

      Version of Record online: 21 JUN 2002 | DOI: 10.1002/pola.10348

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      Poly(n-butyl acrylate)-graft-branched polyethylene was successfully prepared by the combination of two living polymerization techniques. First, a branched polyethylene macromonomer with a methacrylate-functionalized end group was prepared by Pd-mediated living olefin polymerization. The macromonomer was then copolymerized with n-butyl acrylate by atom transfer radical polymerization. Gel permeation chromatography traces of the graft copolymers showed narrow molecular weight distributions indicative of a controlled reaction. The increased viscosity of the reaction solution resulting from increased macromonomer concentrations caused a lowering of the apparent reactivity ratio of the macromonomer to n-butyl acrylate, indicating an incompatibility between nonpolar polyethylene segments and a polar poly(n-butyl acrylate) backbone. The incompatibility was more pronounced in the solid state, exhibiting cylindrical nanoscale morphology as a result of microphase separation, as observed by atomic force microscopy.

    3. Kinetic study of the stable free-radical copolymerization of styrene with butyl methacrylate (pages 2750–2758)

      Rocio Cuervo-Rodriguez, Carmen Fernández-Monreal and Enrique López Madruga

      Version of Record online: 21 JUN 2002 | DOI: 10.1002/pola.10368

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      The stable free-radical copolymerization of styrene with n-butyl methacrylate has been analyzed over a wide range of conversions and monomer feed compositions. The apparent propagation rate coefficients seem to be independent of the monomer feed composition, the number-average molecular weights linearly increase with conversion, and the copolymers present narrow molecular weight distributions. The monomer reactivity ratios have also been determined.

    4. Homopolymerizations and random copolymerizations of olefins with amino-substituted cyclopentadienylchromium complexes (pages 2759–2771)

      Keiji Ogata, Yuushou Nakayama and Hajime Yasuda

      Version of Record online: 24 JUN 2002 | DOI: 10.1002/pola.10365

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      Activities for homopolymerizations of ethylene, propylene, and 1-hexene with the activities for copolymerizations of ethylene with propylene, ethylene with 1-hexene, and propylene with 1-hexene were examined with a variety of half-sandwiched-type chromium complexes. Among them, the (2-N,N-dimethylaminoethyl)indenylchromium dichloride(III) (7)/modified methylaluminoxane (MMAO) system exhibited high activities for copolymerization of ethylene with propylene or 1-hexene in addition to the homopolymerization of ethylene and propylene.

    5. Effect of glyoxylic oxime ether on radical polymerization of styrene (pages 2772–2781)

      Tsuneyuki Sato, Nobuyuki Sato, Makiko Seno and Tomohiro Hirano

      Version of Record online: 24 JUN 2002 | DOI: 10.1002/pola.10357

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      Methyl benzyloxyiminoacetate (MBOIA) as a glyoxylic oxime ether served as a retarder for styrene (St) and as an inhibitor for vinyl acetate in their radical polymerizations, whereas MBOIA showed little effect on the polymerization of methyl methacrylate. The rate constant (kx) of the reaction of MBOIA with polystyrene (PS) radical (PS ·) and the retardation factor (kx/kp) were estimated in the St polymerization at different temperatures. kx = 112 L/mol s and kx/kp = 0.329 at 60 °C. The polymerization system involved electron spin resonance-observable nitrogen-centered radical formed by the reaction of MBOIA with PS ·.

    6. Synthesis and reaction of β-hydroxyaspartic acid-based polymethacrylate (pages 2782–2788)

      Fumio Sanda, Makiko Yokoi, Hiroto Kudo and Takeshi Endo

      Version of Record online: 25 JUN 2002 | DOI: 10.1002/pola.10363

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      O-Methacryloyl-N-(tert-butoxycarbonyl)-β-hydroxyaspartic acid dimethyl ester (MA-B-HAA-M) was synthesized by methyl esterification of β-hydroxyaspartic acid, followed by protection of the amino group with the tert-butoxycarbonyl group and then the reaction of the hydroxyl group with methacryloyl chloride. The monomer efficiently underwent radical polymerization to afford the corresponding polymer [poly(MA-B-H-AA-M)] with a number-average molecular weight of 42,000 in good yields. The alkaline hydrolysis of the polymer occurred not only at the methyl ester but also at the ester moiety between the main and side chains of the polymer. The methyl ester-free polymer gradually released β-hydroxyaspartic acid moiety in a phosphate buffer solution with pH = 7.3 and 7.8.

    7. Maleation of poly(3,4-epoxy-1-butene) for accelerated crosslinking in the presence of a redox catalyst (pages 2789–2798)

      Youngtai Yoo, Larry K. Johnson, Stephen N. Falling, Jeremy R. Lizotte and Timothy E. Long

      Version of Record online: 25 JUN 2002 | DOI: 10.1002/pola.10376

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      Accelerated crosslinking of novel poly(3,4-epoxy-1-butene) (3,4-PEPB) oilgomers in the presence of a cobalt-based redox catalyst was investigated. Novel maleated oligomers offered a unique combination of both electron-rich and electron-poor olefinic sites, and quantitative maleation significantly increased the crosslinking rate of 3,4-PEPB. Efficient copolymerization between terminal maleate groups and olefinic groups in the repeating unit was proposed to account for accelerated crosslinking rates. The addition of novel reactive diluents, such as maleic acid mono-ethyl ester, also effectively improved the 3,4-PEPB crosslinking rate. Observations suggested that a redox process was not a dominant factor in determining crosslinking rates at various experimental conditions.

    8. Atom transfer radical polymerization of acrylates in an ionic liquid: Synthesis of block copolymers (pages 2799–2809)

      Tadeusz Biedroń and Przemysław Kubisa

      Version of Record online: 25 JUN 2002 | DOI: 10.1002/pola.10373

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      Atom transfer radical polymerization (ATRP) of acrylates in ionic liquid, 1-butyl-3-methylimidazolium hexaflurophospate, with the CuBr/CuBr2/amine catalytic system was investigated. Sequential polymerization was performed by synthesizing AB block copolymers. The results suggest that ATRP of butyl acrylate in ionic liquid followed by addition of a second acrylate monomer allows the clean synthesis of block copolymers by one-pot sequential polymerization even if the first stage is carried out to complete conversion of butyl acrylate.

    9. Synthesis and characterization of novel soluble triphenylamine-containing aromatic polyamides based on N,N′-bis(4-aminophenyl)-N,N′-diphenyl-1,4-phenylenediamine (pages 2810–2818)

      Guey-Sheng Liou, Sheng-Huei Hsiao, Mina Ishida, Masaaki Kakimoto and Yoshio Imai

      Version of Record online: 25 JUN 2002 | DOI: 10.1002/pola.10364

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      A new triphenylamine-containing aromatic diamine, N, N′-bis(4-aminophenyl)-N, N′-diphenyl-1,4-phenylenediamine, was prepared by the condensation of N,N′-diphenyl-1,4-phenylenediamine with 4-fluoronitrobenzene, followed by catalytic reduction. A series of novel organosoluble aromatic polyamides with triphenylamine units were prepared from the diamine and various aromatic dicarboxylic acids or their diacid chlorides via the direct phosphorylation polycondensation or low-temperature solution polycondensation.

    10. Emulsion polymerization of styrene using polystyrene-block-poly(ethylene oxide) macromonomers as stabilizers (pages 2819–2827)

      Sébastien Gibanel, Valérie Heroguez and Jacqueline Forcada

      Version of Record online: 26 JUN 2002 | DOI: 10.1002/pola.10379

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      New diblock macromonomers were used as reactive emulsifiers in the emulsion polymerization of styrene. The nature of the reactive group, the molecular weight, the length of the poly(ethylene oxide) block, and the molecular structure of the macromonomer were systematically investigated during this process by analyzing the evolution of the conversion and particle diameters.

    11. Influence of camphorsulfonic acid in nitroxide-mediated styrene miniemulsion polymerization (pages 2828–2841)

      Michael F. Cunningham, Karine Tortosa, Marcus Lin, Barkev Keoshkerian and Michael K. Georges

      Version of Record online: 26 JUN 2002 | DOI: 10.1002/pola.10377

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      The rate-accelerating effects of camphorsulfonic acid (CSA) on nitroxide-mediated styrene miniemulsion polymerization were studied. Polymerizations were initiated with benzoyl peroxide as an initiator and mediated with either 2,2,6,6-tetramethylpiperidinyloxy or 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy. The effects of CSA in miniemulsion on the rate and molecular weight differed from nitroxide-mediated polymerizations in bulk.

    12. Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes (pages 2842–2854)

      Eric F. Connor, Todd R. Younkin, Jason I. Henderson, Sonjong Hwang, Robert H. Grubbs, William P. Roberts and Johnathan J. Litzau

      Version of Record online: 2 JUL 2002 | DOI: 10.1002/pola.10370

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      Neutral Ni(II) salicylaldimine catalysts (pendant ligand = NCMe or PPh3) were used to copolymerize ethylene with monomers containing esters, alcohols, anhydrides, and amides and yielded linear functionalized polyethylene in a single step with no cocatalyst or catalyst additive. A wide range of comonomer incorporation, up to 30 mol %, was achieved while a linear polyethylene microstructure was maintained under mild conditions (40 °C, 100 psi ethylene).

    13. Acid chloride-functionalized hyperbranched polyester for facile and quantitative chain-end modification: One-pot synthesis and structure characterization (pages 2855–2867)

      Nori Yamaguchi, Jin-Shan Wang, J. Michael Hewitt, William C. Lenhart and Thomas H. Mourey

      Version of Record online: 28 JUN 2002 | DOI: 10.1002/pola.10378

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      All-aromatic hyperbranched polyesters with 100% acid chloride functionality were prepared via one-pot thermal homopolymerization of the ultrapure AB2 monomer 5-(trimethylsiloxy)isophthaloyl dichloride between 80 and 200 °C. Because of extremely reactive acid chloride end groups, quantitative and in situ end modification such as esterification could be easily achieved via a clean one-pot, two-step process without any of the side or decomposition reactions often observed in previously reported systems.

    14. Second-harmonic response of a series of chiral polyesters: A joint experimental and theoretical study (pages 2868–2877)

      Biju Philip and K. Sreekumar

      Version of Record online: 28 JUN 2002 | DOI: 10.1002/pola.10371

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      A series of chiral polyesters were synthesized, and their second-harmonic generation efficiency was evaluated by theoretical and experimental means. The second-harmonic generation efficiency is explained as a function of the percentage of the chiral unit in the polymer.

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      Seeded semibatch emulsion polymerization of n-butyl acrylate: Effect of the seed properties (pages 2878–2883)

      C. Plessis, G. Arzamendi, M. Agnely, J. R. Leiza and J. M. Asua

      Version of Record online: 2 JUL 2002 | DOI: 10.1002/pola.10375

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      The effect of the properties of the seed (molecular weight and gel content) on the kinetics and structural properties of the polymer produced by seeded semibatch emulsion polymerization of n-butyl acrylate with potassium persulfate as an initiator at 75 °C was studied. The amount of gel and the molecular weights formed in the process were independent of the initial gel contents present in the seed because the instantaneous generation rate of gel polymer is independent of the gel already present in the polymer particles. On the other hand, when the initial molecular weight of the seed was varied, the fraction of gel and the molecular weights formed were partially affected. A comparison between the experimental and model prediction results is also presented.

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      Well-defined star polylactides and their behavior in two-dimensional chromatography (pages 2884–2887)

      Tadeusz Biela, Andrzej Duda, Stanislaw Penczek, Karsten Rode and Harald Pasch

      Version of Record online: 2 JUL 2002 | DOI: 10.1002/pola.10366

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      Star-shaped polymers bearing three, four, and six poly(L-lactide) (PLA) arms have been prepared starting from trimethylolpropane (3 OH), di(trimethylolpropane) (4 OH), and dipentaerithritol (6 OH) and L,L-dilactide (LA) monomers. Initiator/catalyst tin octoate was used (bulk polymerization, 120 °C). In liquid chromatography at the critical point of adsorption, the elution volumes of the resulting star-shaped PLAs depend exclusively on the number of arms. Thus, in the first dimension of two-dimensional liquid chromatography, it is possible to observe separately various star-shaped polymers. In the second dimension, size exclusion chromatography provides information on the molar masses. Agreement between the assumed and the resulting PLA structures has been confirmed this way.

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    1. Influence of the amine structure on the polymerization of methyl methacrylate photoinitiated by aromatic ketone/amine (pages 2888–2893)

      C. Valderas, S. Bertolotti, C. M. Previtali and M. V. Encinas

      Version of Record online: 2 JUL 2002 | DOI: 10.1002/pola.10382

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      The polymerization of methyl methacrylate photoinitiated by 2-chlorothioxanthone in the presence of amines of different structures has been investigated. Aliphatic hydroxyalkyl amines are more efficient photoinitiators than the corresponding alkyl-substituted compounds. Dimethylanilines with electron-acceptor substituents in the 4-position are better coinitiators than the electron-donor-substituted anilines. Photophysical studies in the polymerization medium have allowed us to simulate the dependence of the photoinitiation efficiency with the amine concentration. Also, photochemical studies have allowed us to establish that the dependence of the polymerization rate on structural features of amines is mainly due to differences in the fraction of produced active radicals that add to the monomer.

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