Journal of Polymer Science Part A: Polymer Chemistry

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

15 October 2001

Volume 39, Issue 20

Pages 3475–3654

  1. Articles

    1. Top of page
    2. Articles
    1. Enlarging the library of poly-(L-lysine citramide) polyelectrolytic drug carriers (pages 3475–3484)

      Anne-Claude Couffin-Hoarau, Mahfoud Boustta and Michel Vert

      Article first published online: 28 AUG 2001 | DOI: 10.1002/pola.1329

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      For the sake of enlargening the family, another route was prospected based on the polycondensation of pentafluorophenyl diester, derived from α-hydroxy acid protected citric acid, and trimethylsilylated diamine, derived from COOH-protected lysine. The resulting polymers were characterized by IR, NMR, and size exclusion chromatographic analyses. Chain structures are also discussed, including the effect of deprotection.

    2. Synthesis, characterization, and electrical properties of nanostructural polyaniline doped with novel sulfonic acids (4-{n-[4-(4-nitrophenylazo)phenyloxy]alkyl}aminobenzene sulfonic acid) (pages 3485–3497)

      Hongjin Qiu and Meixiang Wan

      Article first published online: 23 AUG 2001 | DOI: 10.1002/pola.10002

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      Nanostructures (nanotubes or nanorods) of polyaniline, 100–300 nm in diameter and 10−1 S/cm in maximum conductivity at room temperature, were synthesized with a self-assembly method in the presence of 4-{n-[4-(4-nitrophenylazo)phenyloxy]alkyl}aminobenzene sulfonic acid (Cn-ABSA, where n = 2, 4, 6, 8, or 10). The influence of the number of alkyl groups (n) and the addition of water before polymerization on the morphology, size, and conductivity of the resulting nanostructures was studied. The formation mechanism of the nanostructures was discussed.

    3. Synthesis and characterization of new soluble poly(amide-imide)s derived from 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]hexafluoropropane (pages 3498–3504)

      Der-Jang Liaw, Pei-Nan Hsu, Wen-Hsiang Chen and Been-Yang Liaw

      Article first published online: 30 AUG 2001 | DOI: 10.1002/pola.1330

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      A series of new soluble poly(amide-imide)s were prepared from the diimide-dicarboxylic acid 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]hexafluoropropane (BTPH) with various diamines by direct polycondensation. All the polymers were obtained with inherent viscosities of 0.52–0.86 dL · g−1. These polymers showed an amorphous nature and were readily soluble in various solvents. These polymer films also had tensile strengths of 71–107 MPa and a tensile modulus range of 1.6–2.7 GPa. The glass-transition temperatures of the polymers were determined by a differential scanning calorimetry method, and they ranged from 242 to 279 °C. These poly(amide-imide)s were fairly stable up to a temperature around or above 400 °C, and they lost 10% of their weight from 480 to 536 °C and 486 to 537 °C in nitrogen and air, respectively.

    4. Synthesis of poly(p-phenylene) macromonomers and multiblock copolymers (pages 3505–3512)

      Paul D. Bloom and Valerie V. Sheares

      Article first published online: 31 AUG 2001 | DOI: 10.1002/pola.1331

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      Rigid-rod poly(4′-methyl-2,5-benzophenone) macromonomers were synthesized by Ni(0) catalytic coupling of 2,5-dichloro-4′-methylbenzophenone and end-capping agent 4-chloro-4′-fluorobenzophenone. A flexible, film-forming, multiblock copolymer was synthesized from hydroxy end-capped bisphenol A polyaryletherketone and a poly(4′-methyl-2,5-benzophenone) macromonomer. The polymers were characterized by gel permeation chromatography, DSC, thermogravimetric analysis, and NMR and ultraviolet–visible light spectroscopies.

    5. Modeling molecular weight distribution in emulsion polymerization reactions with transfer to polymer (pages 3513–3528)

      C. Sayer, P. H. H. Araújo, G. Arzamendi, J. M. Asua, E. L. Lima and J. C. Pinto

      Article first published online: 30 AUG 2001 | DOI: 10.1002/pola.10004

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      A mathematical model was developed for the computation of the dynamic evolution of molecular weight distributions (MWDs) during nonlinear emulsion polymerization reactions in the presence of significant chain transfer to polymer. The model was validated with experimental methyl methacrylate/butylacrylate semicontinuous and vinyl acrylate/Veova10 continuous emulsion polymerization results. The model developed is able to represent quite properly the kinetics and MWD of polymer samples during emulsion polymerizations.

    6. Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring-opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes” (pages 3529–3538)

      Michael Möller, Fredric Nederberg, Lisa S. Lim, Rikard Kånge, Craig J. Hawker, James L. Hedrick, Yuedong Gu, Rahul Shah and Nicholas L. Abbott

      Article first published online: 31 AUG 2001 | DOI: 10.1002/pola.10003

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      A general method for the controlled synthesis of polylactide in solution and from solid supports is presented. The evaluation of stannous(II) trifluoromethane sulfonate [Sn(OTf)2] and scandium(III) trifluoromethane sulfonate [Sc(OTf)3] as catalysts for the ring-opening polymerization of L-, D-, and L,D-lactide permits mild, low-temperature, yet highly selective conditions to be developed for the preparation of polylactide brushes attached to gold surfaces.

    7. Synthesis of polymers by template polymerization. I. Template polymerization of poly(methacrylic acid) with β-cyclodextrin (pages 3539–3546)

      Reiko Saito, Yoshiki Okuno and Hiroaki Kobayashi

      Article first published online: 31 AUG 2001 | DOI: 10.1002/pola.10001

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      A novel template monomer having multiple methacryloyl groups was synthesized with β-cyclodextrin by acetylation of primary hydroxyl groups and esterification of secondary hydroxyl groups with methacrylic acid anhydride. The average number of methacrylol groups in the monomer was 11. Radical polymerization of the monomer was carried out. When monomer concentration was smaller than 4.12 × 10−3 M, polymerization was limited inside the molecule, and gelation of the system was hindered. For controlled radical photopolymerization, the methacryloyl groups of the monomer were homogeneously polymerized, and poly(methacrylic acid) with narrow molecular weight distribution was obtained by hydrolysis of polymerized products.

    8. Graft copolymers from star-shaped and hyperbranched polystyrene macromonomers (pages 3547–3555)

      Hasan A. Al-Muallem and Daniel M. Knauss

      Article first published online: 13 SEP 2001 | DOI: 10.1002/pola.10005

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      Star-shaped and hyperbranched polystyrene macromonomers were synthesized by convergent living anionic polymerization and were copolymerized with styrene and methyl methacrylate to form star and hyperbranched graft copolymers. The copolymers were characterized to determine that the macromonomers were incorporated in high yields into the copolymers.

    9. Asymmetric anionic polymerization of N-1-naphthylmaleimide with chiral ligand-organometal complexes in toluene (pages 3556–3565)

      Yukio Isobe, Kenjiro Onimura, Hiromori Tsutsumi and Tsutomu Oishi

      Article first published online: 7 SEP 2001 | DOI: 10.1002/pola.10008

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      Asymmetric anionic homopolymerizations of N-1-naphthylmaleimide (1-NMI) were carried out with chiral ligand/organometal complexes to form optically active polymers. Poly(1-NMI)s obtained with methylene-bridged bisoxazoline derivatives/diethylzinc complexes showed high specific optical rotations ([α]math image) from +152.3 to +191.4°. Circular dichroism spectra of the polymers exhibited a split Cotton effect in the UV absorption-band region. According to the exciton chirality method, the absolute configuration of the polymer main chain was determined in the following manner: (+)-poly[N-substituted maleimides (RMI)] main chains can contain more (S,S)- than (R,R)-configurations. (−)-Poly(RMI) main chains can contain more (R,R)- than (S,S)-configurations.

    10. Possible effects on the polyethene chain structure of trimethylaluminum coordination to zirconocene catalysts (pages 3566–3577)

      Jianke Liu, Jon Andreas Støvneng and Erling Rytter

      Article first published online: 5 SEP 2001 | DOI: 10.1002/pola.10006

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      During polymerization with L2ZrCl2/methylaluminoxane (MAO) catalytic solutions, the molecular weight of polyethene was reduced with the addition of trimethylaluminum (TMA). This effect was much stronger for L = Me5Cp than for L = Cp (where Cp = η5-cyclopentadienyl), in agreement with predictions based on quantum chemical calculations. The addition of TMA to the L = Me5Cp system resulted in a high molecular weight tail in the molecular weight distribution profile, presumably because of a mixture of TMA-sensitive and TMA-insensitive sites.

    11. Synthesis of epoxy monomers that undergo synergistic photopolymerization by a radical-induced cationic mechanism (pages 3578–3592)

      James V. Crivello and Ricardo Acosta Ortiz

      Article first published online: 5 SEP 2001 | DOI: 10.1002/pola.10015

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      The syntheses of a series of novel, cationically photopolymerizable epoxide monomers bearing benzyl ether groups capable of stabilizing free radicals were carried out. These monomers display enhanced reactivity in cationic photopolymerization due to their ability to facilitate the free-radical-induced decomposition of diaryliodonium salt photoinitiators.

    12. Synthesis and properties of oxygen-, methylene-, and alkylene-bridged poly(dithiafulvene)s (pages 3593–3603)

      Sujata Marathe, Takashi Uemura, Kensuke Naka and Yoshiki Chujo

      Article first published online: 7 SEP 2001 | DOI: 10.1002/pola.10012

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      Two aromatic diynes [bis(4-ethynyldiphenyl)methane and 4,4′diethynyldiphenyl ether] were used as starting materials with the aim of obtaining non-π-conjugated methylene- and oxygen-bridged aromatic poly(dithiafulvene)s by cycloaddition polymerization. Further, two aliphatic diynes (1,7-octadiyne and 1,9-decadiyne) were also subjected to cycloaddition polymerization to obtain aliphatic poly(dithiafulvene)s containing localized electron-rich dithiafulvene units. The polymers obtained were characterized by IR, 1H NMR, gel permeation chromatography, and cyclic voltammetery. The electron-donating property of the polymers was evident from the charge-transfer (CT) complex formation with an electron acceptor 7,7,8,8-teracyanoquinodimethane. The CT complexes were characterized by IR, 1H NMR, and ultraviolet–visible spectroscopies.

    13. Decomposition of model alkoxyamines in simple and polymerizing systems. I. 2,2,6,6-tetramethylpiperidinyl- N-oxyl-based compounds (pages 3604–3621)

      Gennady S. Ananchenko and Hanns Fischer

      Article first published online: 13 SEP 2001 | DOI: 10.1002/pola.1332

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      Alkoxyamines labeled TEMPO–R [where TEMPO was 2,2,6,6-tetramethylpiperidinyl-N-oxyl and R was cumyl, 2-tert-butoxy-carbonyl-2-propyl, phenylethyl, 1-tert-butoxy-carbonylethyl (EEst), or 1-methoxycarbonyl-3-methyl-3-phenylbutyl] yielded mainly alkenes and 1-hydroxy-2,2,6,6-tetramethylpiperidine (TEMPOH). For all radicals R and their styrene adducts, this occurred to a minor extent (0.6–3%) by bulk disproportionation that paralleled recoupling, but for methyl methacrylate adducts, this occurred to a considerable degree (≥20%). TEMPO–EEst (but not the other alkoxyamines) also exhibited substantial nonradical decay to the alkene and TEMPOH.

    14. Synthesis and characterization of novel polyimides containing stilbene unit in the side chain and their controllability of nematic liquid crystal alignment on the rubbed surfaces (pages 3622–3632)

      J. H. Park, J. C. Jung, B.-H. Sohn, S. W. Lee and M. Ree

      Article first published online: 10 SEP 2001 | DOI: 10.1002/pola.10010

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      Four polyimides containing hexylene spacer and a fluorostilbene unit in the side chains were prepared in thin-film form by two-step condensation of 3,3′-bis[(4′-fluoro-4-stilbenyl)oxyhexyloxy]-4,4′-biphenyldiamine (FS6B) with pyromellitic dianhydride (PMDA), benzophenone-3,3′,4,4′-tetracarboxylic dianydride (BTDA), 4,4′-oxydi(phthalic anhydride) (ODPA), and 4,4′-hexafluoroisopropylidenedi(phthalic anhydride) (6FDA), respectively, and their controllability of liquid crystal (LC) alignment on rubbed surfaces was investigated. Pretilt angles of LCs were achieved in the 2–9° range, depending on the rubbing density and backbone structures. The effect of the mesogenic stilbene group on the pretilting of LCs was distinctive in FS6B-PMDA. Contact-angle measurements on thin films annealed at 120 °C revealed that FS6B-PMDA potentially had the better alignment stability than FS6B-6FDA.

    15. Role of grafting in the emulsion polymerization of vinyl acetate with poly(vinyl alcohol) as an emulsifier. I. Effect of the degree of blockiness on the kinetics and mechanism of grafting (pages 3633–3654)

      B. M. Budhlall, E. D. Sudol, V. L. Dimonie, A. Klein and M. S. El-Aasser

      Article first published online: 10 SEP 2001 | DOI: 10.1002/pola.10016

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      The kinetics of the emulsion polymerization of vinyl acetate were monitored, and the evolution of the amounts of grafted poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc) was determined in polymerizations employing PVAs differing in their degrees of blockiness. The amounts of grafted PVAc were about the same as those in the final latexes (37–39%). In contrast, the grafting of the blockier PVA was about one-third the grafting of the more random PVA (∼10% vs ∼30%).