Journal of Polymer Science Part A: Polymer Chemistry

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

1 May 2002

Volume 40, Issue 9

Pages 1209–1377

  1. Articles

    1. Top of page
    2. Articles
    3. Erratum
    1. Novel tricontinuous hydrophilic–lipophilic–oxyphilic membranes: Synthesis and characterization (pages 1209–1217)

      Pious Kurian and Joseph P. Kennedy

      Version of Record online: 6 MAR 2002 | DOI: 10.1002/pola.10209

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      Novel tricontinuous membranes consisting of well-defined hydrophilic poly(ethylene glycol) (PEG) and lipophilic polyisobutylene (PIB) segments crosslinked by oxyphilic poly(pentamethylcyclopentasiloxane) (PD5) domains have been synthesized and characterized. Tricontinuity arises because the three membrane constituents—PEG, PIB, and PD5—are mutually incompatible and give rise to three independent cocontinuous phases (channels). The continuous PEG segments impart swelling in water (hydrogel character), the rubbery PIB moieties provide strength, and the PD5 domains provide crosslinking and enhanced O2 permeability. The synthesis involves the random cohydrosilation of various lengths (number-average molecular weights) of α,ω-diallyl-PEG and α,ω-diallyl-PIB segments by pentamethylcyclopentasiloxane (D5H) followed by water-mediated oxidation of the SiH groups of the D5H to SiOH groups, which immediately polycondense to PD5 domains.

    2. Synthesis of biodegradable amphiphilic AB-type diblock copolymers of lactide and depsipeptide with pendant reactive groups (pages 1218–1225)

      Tatsuro Ouchi, Hidetake Miyazaki, Hidetoshi Arimura, Fumitaka Tasaka, Atsushi Hamada and Yuichi Ohya

      Version of Record online: 7 MAR 2002 | DOI: 10.1002/pola.10211

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      The syntheses of amphiphilic AB-type diblock copolymers composed of hydrophobic polylactide segment and hydrophilic polydepsipeptide segment with amino or carboxyl groups were performed. After the terminal hydroxyl groups of the protected polydepsipeptides poly[Glc-Lys(Z)] and poly[Glc-Asp(OBzl)] (where Glc is glycolic acid, Lys is lysine, Asp is aspartic acid, Z is benzyloxycarbonyl, and OBzl is benzyl) were converted into the potassium alcoholates with K/naphthalene, L-lactide was polymerized in the presence of the corresponding polymeric alcoholates as macroinitiators in tetrahydrofuran to obtain poly[Glc-Lys(Z)]-block-poly(L-lactide) and poly[Glc-Asp(OBzl)]-block-poly(L-lactide). Subsequent deprotection of benzyl-oxycarbonyl (Z) and benzyl (OBzl) groups gave the objective amphiphiles poly(Glc-Lys)-block-poly(L-lactide) and poly(Glc-Asp)-block-poly(L-lactide), respectively.

    3. Solid polymer electrolytes. IV. Preparation and characterization of novel crosslinked epoxy-siloxane polymer complexes as polymer electrolytes (pages 1226–1235)

      Wuu-Jyh Liang, Chao-Ling Kuo, Chia-Liang Lin and Ping-Lin Kuo

      Version of Record online: 7 MAR 2002 | DOI: 10.1002/pola.10204

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      Two series of novel crosslinked siloxane-based polymers and their complexes with lithium perchlorate (LiClO4) were prepared and characterized by Fourier transform infrared spectroscopy, solid-state NMR (13C, 29Si, and 7Li nuclei), and differential scanning calorimetry. Their thermal stability and ionic conductivity of these complexes were also investigated by thermogravimetric and AC impedance measurements. In these polymer networks, poly(propylene oxide) (PPO) chains with different molecular weights were introduced through self-synthesized epoxy-siloxane precursors cured with two curing agents. The glass-transition temperature (Tg) of these copolymers is dependent on the length of the ether units. The dissolution of LiClO4 considerably increases the Tg of the polyether segments. The dependence of the ionic conductivity was investigated as a function of temperature, LiClO4 concentration, and the molecular weight of the polyether segments. The ion-transport behavior was affected by the combination of the ionic mobility and the number of carrier ions. The 7Li solid-state NMR line shapes of these polymer complexes suggest a significant interaction between Li+ ions and the polymer matrix, and temperature- and LiClO4 concentration-dependent chemical shifts are correlated with ionic conductivity.

    4. Simultaneous construction of the polymer backbone and side chains by three-component polycondensation: The synthesis of polyurethanes with allyl side chains from dialdehydes, alkylene N,N′-bis(trimethylsilyl) carbamates, and allyltrimethylsilane (pages 1236–1242)

      Lui Niimi, Ken-Ichi Serita, Shuichi Hiraoka and Tsutomu Yokozawa

      Version of Record online: 8 MAR 2002 | DOI: 10.1002/pola.10208

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      Polyurethanes with allyl side chains were synthesized by the simultaneous acid-catalyzed reaction of dialdehydes, alkylene N,N′-bis(trimethylsilyl) carbamates, and allyltrimethylsilane. When mixtures of these three monomers were added to the catalyst, the desired polyurethanes were obtained in good yields.

    5. Benzoyl peroxide-initiated copolymerization of citronellol and vinyl acetate (pages 1243–1252)

      Prachi Pandey and A. K. Srivastava

      Version of Record online: 8 MAR 2002 | DOI: 10.1002/pola.10173

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      The radical copolymerization of citronellol with vinyl acetate (VA) in xylene at 60 ± 0.1 °C for 90 min in the presence of benzoyl peroxide follows ideal kinetics and results in the formation of an alternating copolymer as demonstrated by the values of the reactivity ratios [r1 (VA) = 0.02 and r2 (citronellol) = 0.0002], which have been calculated with the Kelen–Tüdos method. The overall activation energy is computed to be 75 kJ/mol. The IR spectrum of the copolymer shows the presence of bands at 3400 cm−1 due to an alcoholic group and 1750 cm−1 due to a 〉C[DOUBLE BOND]O group. The values of the Mark–Houwink constants for this copolymer system have been determined with gel permeation chromatography to be α = 0.375 and K = 2.4 × 10−4. The glass-transition temperature, determined with differential scanning calorimetry, is 68.32 °C. The mechanism has been elucidated.

    6. Synthesis of amphiphilic block–graft copolymers [poly(styrene-b-ethylene-co-butylene-b-styrene)-g-poly(acrylic acid)] and their aggregation in water (pages 1253–1266)

      Fanglin Ning, Ming Jiang, Minfang Mu, Hongwei Duan and Jingwei Xie

      Version of Record online: 12 MAR 2002 | DOI: 10.1002/pola.10190

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      Novel block–graft copolymers [poly(styrene-b-ethylene-co-butylene-b-styrene)-g-poly(tert-butyl acrylate)] with controllable graft densities and average graft-chain lengths were synthesized by atom transfer radical polymerization. The poly(tert-butyl acrylate) grafts were easily converted into poly(acrylic acid). A preliminary study of the aggregation of a novel block–graft amphiphile [poly(styrene-b-ethylene-co-butylene-b-styrene)-g-poly(acrylic acid)] in water showed a variety of morphologies.

    7. One-step synthesis of polycarbonates bearing pendant carboxyl groups by lipase-catalyzed ring-opening polymerization (pages 1267–1274)

      Talal F. Al-Azemi and Kirpal S. Bisht

      Version of Record online: 12 MAR 2002 | DOI: 10.1002/pola.10212

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      The ring-opening polymerization of a monomer containing a free carboxylic acid group is reported for the first time. The monomer, 5-methyl-5-carboxyl-1,3-dioxan-2-one (MCC), was copolymerized with trimethylene carbonate (TMC) in an enzymatic ring-opening polymerization conducted in bulk at 80 °C. 13C NMR spectral data were used for microstructural analysis, which suggested the formation of random, linear, and pendant carboxylic acid groups containing polycarbonates with hydroxyl groups at both chain ends. The products may provide numerous opportunities for further modifications.

    8. Emulsion copolymerization of vinylidene chloride and methyl methacrylate. I. Effects of operating variables on the kinetic behavior (pages 1275–1284)

      M. Nomura, H. Sakai, Y. Kihara and K. Fujita

      Version of Record online: 12 MAR 2002 | DOI: 10.1002/pola.10206

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      The kinetics and mechanisms of the emulsion copolymerization of vinylidene chloride and methyl methacrylate was investigated at 50 °C with sodium lauryl sulfate as an emulsifier and potassium persulfate as an initiator, respectively. The effects of initial emulsifier (So) and initiator (Io) concentrations on the rate of copolymerization, Rpt and the number of polymer particles produced, NT were summarized by the following equations: Rpt∝ Smath imageI math image, NT ∝ Smath imageI math image On the other hand, the weight fraction of methyl methacrylate in the initial monomer charge Φ gave a reverse effect on Rpt and NT, as shown in the figure.

    9. Poly(pentamethylcyclopentasiloxane). I. Synthesis and characterization (pages 1285–1292)

      P. Kurian, J. P. Kennedy, A. Kisluik and A. Sokolov

      Version of Record online: 13 MAR 2002 | DOI: 10.1002/pola.10213

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      Pentamethylcyclopentasiloxane (D5H) can be readily polymerized to poly(pentmethylcyclopentasiloxane) (PD5) with a Pt-based (Karstedt) catalyst in the presence of water in bulk or in solution. The polymerization starts with the oxidation of the SiH groups by water into an intermediate containing SiOH groups (SiH + H2O [RIGHTWARDS ARROW] SiOH + H2), which is followed immediately by the condensation (2SiO [RIGHTWARDS ARROW] Si[BOND]O[BOND]Si) of D5H rings into complex aggregates of cyclosiloxane moieties. The product is a solid with extraordinary properties: it is a stiff and brittle solid, is insoluble in common solvents, does not exhibit a melting endotherm but has an extremely low glass transition (Tg,PD5 = −151 ± 0.5 °C), and is thermally stable up to at least 700 °C. Brillouin scattering indicates very slow variation of the relaxation time with temperature, a property characteristic of strong glass-forming systems such as silica glass.

    10. Synthesis and photochemical reaction of cyclic oligomers: Synthesis and photopolymerization of novel C-methylcalix[4]resorcinarene and p-alkylcalix[n]arene derivatives containing spiro ortho ether groups (pages 1293–1302)

      Tadatomi Nishikubo, Atsushi Kameyama, Hiroto Kudo and Kousuke Tsutsui

      Version of Record online: 13 MAR 2002 | DOI: 10.1002/pola.10207

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      Certain new photoreactive calixarene derivatives (3a–3c) containing spiro ortho ester groups were synthesized by the reaction of calixarene derivatives (2a–2c) containing pendant carboxyl groups with 2-bromomethyl-1,4,6-trioxaspiro[4.4]nonane. The synthesized calixarene derivatives, containing spiro ortho ester groups, had relatively good thermal stability. The photoinitiated cationic polymerization of the spiro ortho ester groups in the calixarene derivatives was examined, and it was found that the reaction did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating.

    11. Functionalization of polyethylene with silane comonomers (pages 1303–1308)

      S. Lipponen and J. Seppälä

      Version of Record online: 13 MAR 2002 | DOI: 10.1002/pola.10215

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      We synthesized a new monomer with a reactive phenylsilane group that is an intermediate for many functional groups. Electropositive silicon had no negative effect on the copolymerization with ethylene and metallocene catalysts, and this enabled the incorporation of functional groups into polyethylene without the loss of catalyst activity and comonomer reactivity or a drastic drop in molar mass.

    12. Production of crosslinked, hollow nanoparticles by surface-initiated living free-radical polymerization (pages 1309–1320)

      Susanne Blomberg, Sofia Ostberg, Eva Harth, Anton W. Bosman, Brooke Van Horn and Craig J. Hawker

      Version of Record online: 13 MAR 2002 | DOI: 10.1002/pola.10210

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      Surface-initiated living free-radical polymerization is employed in a multistep procedure to prepare hollow polymeric nanocapsules. Initially, alkoxyamine initiating groups are attached to the surface of silica particles; then, functionalized linear chains are grown from these initiating sites. The choice of functional groups is governed by their ability to undergo facile coupling to yield a crosslinked polymeric shell covalently attached to the central silica core. Dissolution of the silica core gives the hollow polymeric nanocapsules, which are stable under solvent dissolution and thermal treatment.

    13. Synthesis of novel nitrogen- and sulfur-containing conjugated polymers used as hole-transporting materials for organic light-emitting diodes (pages 1321–1333)

      Kaizheng Zhu, Zhiyuan Xie, Lixiang Wang, Xiabin Jing and Fosong Wang

      Version of Record online: 14 MAR 2002 | DOI: 10.1002/pola.10214

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      Two series of highly soluble new nitrogen- and sulfur-containing conjugated polymers were synthesized via an acid-induced self-polycondensation of functional monomers with methyl sulfinyl and aromatic groups. These polymers were used as hole-transport layers (HTL) in two-layer light-emitting diodes ITO/HTL/Alq/Mg:Ag [ITO = indium tin oxide, and Alq = tris(8-quinolinato)aluminum]. The typical turn-on voltage of these diodes is about 4–5 V. The maximum brightness of the device was about 3440 cd/m2 at 20 V. The maximum efficiency was estimated to be 0.15 lm/W at 10 V.

    14. Synthesis of hydroxy-terminated, oligomeric poly(silarylene disiloxane)s via rhodium-catalyzed dehydrogenative coupling and their use in the aminosilane–disilanol polymerization reaction (pages 1334–1341)

      Craig L. Homrighausen and Teddy M. Keller

      Version of Record online: 14 MAR 2002 | DOI: 10.1002/pola.10110

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      A series of oligomeric, hydroxy-terminated silarylene–siloxane prepolymers of various lengths were prepared via dehydrogenative coupling between 1,4-bis(dimethylsilyl)benzene [H(CH3)2SiC6H4Si(CH3)2H] and excess 1,4-bis(hydroxydimethylsilyl)benzene [HO(CH3)2SiC6H4Si(CH3)2OH] in the presence of a catalytic amount of Wilkinson's catalyst [(Ph3P)3RhCl]. The diacetylene units were incorporated into the polymer main chain via aminosilane–disilanol polycondensation between 1,4-bis(dimethylaminodimethylsilyl)butadiyne [(CH3)2N[BOND]Si(CH3)2[BOND]C[TRIPLE BOND]C[BOND]C [TRIPLE BOND]C[BOND](CH3)2SiN(CH3)2] and the hydroxy-terminated prepolymers.

    15. Synthesis and characterization of micrometer-sized particles of narrow size distribution with chloromethyl functionality on the basis of single-step swelling of uniform polystyrene template microspheres (pages 1342–1352)

      Michal Kedem and Shlomo Margel

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/pola.10219

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      Crosslinked and noncrosslinked micrometer-sized polystyrene/polychloromethylstyrene uniform composite particles of controlled properties were prepared by a single-step swelling process of polystyrene template microspheres.

    16. Hydrogen effects in propylene polymerization reactions with titanium-based Ziegler–Natta catalysts. I. Chemical mechanism of catalyst activation (pages 1353–1365)

      Yury V. Kissin and Laura A. Rishina

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/pola.10225

      A new mechanism for the hydrogen activation effect in propylene polymerization reactions with Ti-based Ziegler–Natta catalysts is proposed. A propylene polymerization reaction occasionally leads to the formation of a dormant center incapable of propylene insertion, the Ti[BOND]CH(CH3)2 species:

      • equation image


      • equation image

      Hydrogen reacts with the Ti[BOND]CH(CH3)2 species and generates the Ti[BOND]H bond. The latter predominantly inserts propylene in the primary orientation and so reactivates the center:

      • equation image

      Ethylene can insert into the Ti[BOND]CH(CH3)2 species, although relatively slowly (this reaction accounts for the ethylene activation effect in propylene polymerization reactions):

      • equation image

      Polymer molecules generated in a series of steps starting with the latter reaction were observed in low molecular weight fractions of ethylene/α-olefin copolymers produced with Ti-based catalysts.

    17. Kinetics of alpha-methylstyrene oligomerization by catalytic chain transfer (pages 1366–1376)

      A. A. Gridnev

      Version of Record online: 15 MAR 2002 | DOI: 10.1002/pola.10220

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      Alpha-methylstyrene (AMS) can be effectively dimerized by a free-radical mechanism mediated by the catalytic chain transfer (CCT). Above the ceiling temperature of AMS, 61 °C, the dimer may become almost an exclusive product with only a small percentage of impurity of AMS trimer and tetramer. Kinetics of the AMS oligomerization has two characteristic features. First, the rate of the oligomerization increases with concentration of the CCT catalyst. Second, conversion reaches a plateau at 60–70%. A kinetic scheme explained both effects. Besides AMS, para- and methasubstituted AMS can also be dimerized. Orthosubstituted AMS's do not oligomerize.

  2. Erratum

    1. Top of page
    2. Articles
    3. Erratum
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