Journal of Polymer Science Part A: Polymer Chemistry

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

1 November 2003

Volume 41, Issue 21

Pages 3197–3467

  1. Editorial

    1. Top of page
    2. Editorial
    3. Highlight
    4. Articles
    5. Rapid Communication
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      Editorial announcement (page 3197)

      Mitsuo Sawamoto, Craig J. Hawker and Karen L. Wooley

      Version of Record online: 12 SEP 2003 | DOI: 10.1002/pola.10966

  2. Highlight

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    2. Editorial
    3. Highlight
    4. Articles
    5. Rapid Communication
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      Modular approach for novel nanostructered polycondensates enabled by the unique selectivity of carbonyl biscaprolactam (pages 3198–3205)

      Ton Loontjens

      Version of Record online: 11 SEP 2003 | DOI: 10.1002/pola.10912

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      Because of the high investment hurdles to produce new polymers, we developed new enabling chemistries to produce novel well-defined polymeric materials by the addition of small amounts of functional reactive compounds to standard polymers during regular processing steps. We found that carbonyl biscaprolactam and its derivatives couple in a strictly linear fashion polymer chains. The breakthrough came when we found that many building blocks, provided with functional groups, could be made and built into polymeric materials to improve the polymer properties substantially.

  3. Articles

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    2. Editorial
    3. Highlight
    4. Articles
    5. Rapid Communication
    1. Synthesis of poly(tetrahydrofuran)-b-polystyrene block copolymers from dual initiators for cationic ring-opening polymerization and atom transfer radical polymerization (pages 3206–3217)

      Katrien V. Bernaerts, Etienne H. Schacht, Eric J. Goethals and Filip E. Du Prez

      Version of Record online: 9 SEP 2003 | DOI: 10.1002/pola.10921

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      The dual initiator 4-hydroxy-butyl-2-bromoisobutyrate has been prepared and used for the preparation of homopolymers and block copolymers by the combination of the cationic ring-opening polymerization (CROP) of tetrahydrofuran (THF) and the atom transfer radical polymerization (ATRP) of styrene. The dual initiator contains a bromoisobutyrate initiating site for the ATRP of styrene and a hydroxyl group for the initiation of the CROP of THF. The preparation of block copolymers from PS-OH (polystyrene with hydroxyl groups) and PTHF-Br [poly(tetrahydrofuran) with tertiary bromide end groups] macroinitiators for the CROP of THF and the ATRP of styrene, respectively, has been investigated.

    2. Effects of clay-modifying agents on the morphology and properties of poly(methyl methacrylate)/clay nanocomposites synthesized via γ-ray irradiation polymerization (pages 3218–3226)

      Wei'an Zhang, Ying Liang, Wei Luo and Yue'e Fang

      Version of Record online: 8 SEP 2003 | DOI: 10.1002/pola.10919

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      Intercalated and partially exfoliated poly(methyl methacrylate) (PMMA)/clay nanocomposites were obtained with nonreactive and reactive clay, respectively. The character of the clay was dependent on the corresponding clay-modifying agent. The effects of the clay-modifying agents on the thermal and mechanical properties of PMMA/clay nanocomposites were also investigated. The thermal properties of exfoliated PMMA/clay nanocomposites were much more distinctly enhanced by the clay-modifying agents because of the chemical bond that formed between the intercalating agents of the clay and the chains of PMMA. Moreover, PMMA/clay nanocomposites were prepared by a γ-ray irradiation technique.

    3. Design and synthesis of highly photopolymerizable styrenyl compounds in solid-state photoinitiated polymerization (pages 3227–3242)

      Akira Furukawa, Yukio Imanishi and Masao Tanihara

      Version of Record online: 8 SEP 2003 | DOI: 10.1002/pola.10915

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      A series of styrenyl compounds bearing 1,3,4-thiadiazole groups were prepared, and their photopolymerization behavior was investigated in polymer matrices. They exhibited considerably higher polymerization rates than those of other styrenyl compounds and a conventional acrylic monomer (trimethylolpropane triacrylate). These high polymerizabilities were attributed to the aggregated states of the styrenyl compounds in polymer matrices caused by strong intermolecular interactions.

    4. Crosslinking polymerization leading to interpenetrating polymer network formation. II. Polyaddition crosslinking reactions of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with various diols (pages 3243–3248)

      Tadahiro Kiguchi, Hiroyuki Aota and Akira Matsumoto

      Version of Record online: 8 SEP 2003 | DOI: 10.1002/pola.10917

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      The polyaddition crosslinking reactions of multifunctional poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with ethylene glycol (EG), 1,6-hexane diol, and 1,10-decane diol (DD) resulting in polyurethane networks were investigated. The deviation of the actual gel point from the theoretical one was smaller from EG to DD. The intrinsic viscosity of resulting prepolymer exhibited almost no variation with progressing polymerization for the EG system, whereas it gradually increased with conversion for the DD system. The swelling ratio of the resulting gel was higher from EG to DD. These are discussed mechanistically in terms of the significant occurrence of intramolecular cyclization and intramolecular crosslinking reactions leading to shrinkage of the molecular size.

    5. Polyimides from isomeric oxydiphthalic anhydrides (pages 3249–3260)

      Qingxuan Li, Xingzhong Fang, Zhen Wang, Lianxun Gao and Mengxian Ding

      Version of Record online: 9 SEP 2003 | DOI: 10.1002/pola.10918

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      Polyimides from isomeric oxydiphthalic anhydrides (ODPAs) with several diamines were prepared in DMAc by the conventional two-step method. Tg's followed to the decrease order of polyimides based on 2,2′,3,3′-ODPA, 2,3,3′,4′-ODPA, and 3,3′,4,4′-ODPA. 2a, 2b, 3a, and 3b have good solubility in polar aprotic solvents and their films soften rapidly beyond Tg's when stretching at 3 °C/min. 3a has the lowest melt viscosity compared with 2a and 4a.

    6. Compositional heterogeneity effects in multisticker associative polyelectrolytes prepared by micellar polymerization (pages 3261–3274)

      Piotr Kujawa, Annie Audibert-Hayet, Joseph Selb and Françoise Candau

      Version of Record online: 8 SEP 2003 | DOI: 10.1002/pola.10866

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      An aqueous micellar radical polymerization technique has been used to prepare water-soluble polyelectrolytes of acrylamide (AM), sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) and hydrophobic N,N-dihexylacrylamide (DiHexAM). These polymers exhibit an appreciable compositional heterogeneity, in contrast to their neutral analogues. The drift in composition is attributed to the electrostatic repulsion between the negatively charged growing polymeric chains and the anionic sodium dodecyl sulfate micelles, inside of which the hydrophobic monomer is entrapped. An optimization of the polymerization process gives terpolymers of homogeneous composition. These hydrophobically-modified polyelectrolytes are multisticker associative polymers whose thickening ability is directly affected by the extent of their compositional heterogeneity.

    7. Morphology of poly(p-oxybenzoyl) crystal prepared by direct polycondensation of p-hydroxybenzoic acid with p-toluenesulfonyl chloride in pyridine (pages 3275–3282)

      Kunio Kimura, Toshiyuki Horii and Yuhiko Yamashita

      Version of Record online: 10 SEP 2003 | DOI: 10.1002/pola.10916

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      Sheaflike lozenge-shaped poly(p-oxybenzoyl) crystals were prepared with the reaction-induced crystallization of oligomers during the direct polycondensation of p-hydroxybenzoic acid with p-toluenesulfonyl chloride and N,N-dimethylformamide in pyridine. When the number-average degree of polymerization of the oligomers exceeded a critical value of about 4, they were precipitated to form the hexagonal lamellae. The crystals were grown very quickly to lozenge-shaped crystal through screw dislocation with the continuous precipitation of oligomers from the solution. The further polymerization occurred in the precipitated crystal with developing polymer-chain packing.

    8. Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2-aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism (pages 3283–3299)

      Virgil Percec, Anatoliy V. Popov, Ernesto Ramirez-Castillo and Oliver Weichold

      Version of Record online: 11 SEP 2003 | DOI: 10.1002/pola.10937

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      The first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu0 produced by the disproportionation of CuI in the presence of strongly CuII binding ligands such as tris(2-aminoethyl)amine (TREN) or polyethyleneimine (PEI). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu0 and degenerative chain transfer.

    9. Thermosensitive polyalcohols: Synthesis via living cationic polymerization of vinyl ethers with a silyloxy group (pages 3300–3312)

      Shinji Sugihara, Kiyotaka Hashimoto, Yuko Matsumoto, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 11 SEP 2003 | DOI: 10.1002/pola.10929

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      Thermosensitive homopoly(vinyl ether)s and copoly(vinyl ether)s with hydroxy groups were synthesized via the living cationic polymerization of Si-containing vinyl ethers. An appropriate hydrophilic/hydrophobic balance was found to be the key to sensitive phase separation. Among the homopolyalcohols studied, only poly(4-hydroxybutyl vinyl ether) underwent lower-critical-solution-temperature-type thermally induced phase separation in water, and this made it possible to prepare novel thermosensitive block and random copolymers consisting solely of alcohol units.

    10. Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst (pages 3313–3319)

      Yongxin Qin, Tao Tang, Zhongfu Zhao and Baotong Huang

      Version of Record online: 11 SEP 2003 | DOI: 10.1002/pola.10925

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      Porous polystyrene particles were prepared and applied as supports for metallocene catalyst. The metallocene was anchored not only on the surface but also inside the pores or tunnels of the support, and the support particles underwent fragmentation during the polymerization process. This played a decisive role in the activity of the supported catalyst as well as the morphology of the polyethylene obtained.

    11. Photoinitiated cationic polymerization of monofunctional benzoxazine (pages 3320–3328)

      Fatmanur Kasapoglu, Ioan Cianga, Yusuf Yagci and Tsutomu Takeichi

      Version of Record online: 12 SEP 2003 | DOI: 10.1002/pola.10913

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      The photoinitiated ring-opening cationic polymerization of a monofunctional benzoxazine, 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine, with onium salts such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate as initiators was examined. The structures of the polymers thus formed were complex and related to the ring-opening process of the protonated monomer either at the oxygen or nitrogen atoms. The phenolic mechanism also contributed, but its influence decreased with decreasing monomer concentration. Thermal properties of the polymers were also investigated by differential scanning calorimetry and thermogravimetric analysis.

    12. Complex polymer architectures through dimethoxymethyl 1,1-diphenylethylene derivatives (pages 3329–3335)

      Nicolas Meyer, Mohamad Nasser Eddine, Christelle Delaite, Guy Hurtrez and Philippe Dumas

      Version of Record online: 12 SEP 2003 | DOI: 10.1002/pola.10898

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      Polystyryl reacted on dimethoxymethyl 1,1-diphenylethylene and formed complex polymer architectures according to the medium polarity. In a polar medium (a), a double-addition/elimination occurred on each di-MeO-phenyl moiety, leading to a PS3 star and, subsequently, to a PS6 star. In a nonpolar medium (b), successive nucleophilic substitutions led to a hyperbranched structure.

    13. Simplified synthesis of carbohydrate-functional siloxanes via transacetalation. I. Glucose-functional siloxanes (pages 3336–3345)

      Takuya Ogawa

      Version of Record online: 16 SEP 2003 | DOI: 10.1002/pola.10926

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      Carbohydrate-functional siloxanes (CHFSs) have been synthesized by a simplified two-step reaction with easily available compounds: Si[BOND]H-functional siloxanes and unmodified glucose. The advantages of this process include the low cost of the materials, few synthetic steps, and high yields. The first step, hydrosilylation, which yields acetal-functional siloxanes, proceeds quantitatively, whereas the second step, transacetalation, which yields CHFSs, is limited by the structure of the siloxane backbone. The CHFSs obtained in this study exhibit good solubility in polar solvents such as dimethylformamide and dimethyl sulfoxide and in nonpolar solvents, and this indicates that these materials are amphiphilic in nature.

    14. Synthesis and characterization of poly(methyl methacrylate)/casein nanoparticles with a well-defined core-shell structure (pages 3346–3353)

      Junmin Zhu and Pei Li

      Version of Record online: 16 SEP 2003 | DOI: 10.1002/pola.10920

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      Well-defined core-shell poly(methyl methacrylate)/casein nanoparticles were prepared via a direct graft copolymerization of methyl methacrylate from casein induced by a small amount of alkyl hydroperoxide in water at 80 °C.

    15. Synthesis and chiral recognition ability of optically active poly{N-[(R)-α-methoxycarbonylbenzyl]methacrylamide} with various tacticities by radical polymerization using Lewis acids (pages 3354–3360)

      Kohei Morioka, Yoshikatsu Suito, Yutaka Isobe, Shigeki Habaue and Yoshio Okamoto

      Version of Record online: 16 SEP 2003 | DOI: 10.1002/pola.10927

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      The radical polymerization of an optically active methacrylamide with (R)-phenylglycine methyl ester, N-[(R)-α-methoxycarbonylbenzyl]methacrylamide (MCBMAM), was carried out in the absence and presence of various Lewis acids. The polymerization of MCBMAM in the presence of Lewis acids gave polymers with much higher isotacticity than those obtained without the acids. The stereoregularity of these polymers influenced the chiral recognition ability.

    16. Synthesis and characterization of novel polyimides with 2,2-bis[4(4-aminophenoxy)phenyl]phthalein-3′,5′-bis(trifluoromethyl)anilide (pages 3361–3374)

      B. Y. Myung, J. S. Kim, J. J. Kim and T. H. Yoon

      Version of Record online: 18 SEP 2003 | DOI: 10.1002/pola.10924

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      A novel diamine monomer, 2,2-bis[4(4-aminophenoxy)phenyl]phthalein-3′,5′-bis(trifluoromethyl)anilide (6FADAP) was synthesized via the Williamson ether condensation reaction from 1-chloro-4-nitrobenzene and phenolphthalein-3′,5′-bis(trifluoromethyl)anilide (6FAP), followed by hydrogenation. The monomer was characterized by Fourier transform infrared (FTIR), 1H NMR, 19F NMR, elemental analysis (EA), and titrator, and then utilized to prepare polyimides with 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA). The polyimides were characterized by FTIR, NMR, gel permeation chromatography (GPC), differential scanning calorimetry, and thermogravimetric analysis. Their solubility, water absorption, CTE, dielectric constant, and refractive index were also evaluated. The polyimides prepared with 6FADAP provided excellent solubility, high glass-transition temperature (290 °C), good thermal stability (>500 °C in air), low water absorption (1.9 wt %), a low dielectric constant (2.81), a low refractive index, and low birefringence (0.0041).

    17. Synthesis and characterization of liquid-crystalline epoxy and its blend with conventional epoxy (pages 3375–3383)

      K. Sadagopan, D. Ratna and A. B. Samui

      Version of Record online: 18 SEP 2003 | DOI: 10.1002/pola.10923

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      Liquid-crystalline (LC) epoxy was synthesized by reacting terephthaloyl bis(4-oxy benzoic acid) with diglycidyl ether of bisphenol A (DGEBA) epoxy. The incorporation of LC epoxy in the DGEBA matrix resulted in an increased dynamic modulus and a reduction in the glass-transition temperatures.

    18. Synthesis and crosslinking of biphenyl and naphthalene liquid-crystalline polyethers with pendant full-saturated and vinyl-terminated aliphatic chains (pages 3384–3399)

      Lourdes Callau, José Antonio Reina and Ana Mantecón

      Version of Record online: 19 SEP 2003 | DOI: 10.1002/pola.10934

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      Two series of vinyl-terminated, side-chain liquid-crystalline polyethers containing 4,4′-biphenyl and 2,6-naphthalene moieties with several contents of vinyl groups were synthesized by chemically modifying PECH with mixtures of saturated and vinyl-terminated acids. The mesomorphic behavior of the polymers was studied by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. The crosslinking of most polymers was done by peroxide-type initiators, which generally led to liquid-crystal elastomers. The mesophase organization was maintained on the crosslinked materials.

    19. Metalization of polypropylene. I. Synthesis and melt free-radical grafting of novel maleimides and methacrylates containing chelating moieties (pages 3400–3413)

      Simone Knaus, Alexander Liska and Peter Sulek

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10938

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      Several monomers containing functional groups capable of the chemisorption of palladium, a determinant step in the electroless metalization of polymers, were prepared. A long-chain aliphatic spacer was introduced to increase the solubility of the monomers in the polymer melt and to enhance the compatibility of grafted side chains and homopolymers with polypropylene (PP). PP was functionalized by reactive extrusion and injection molding, and some properties of the modified polymer were investigated. Preliminary metalization experiments showed the feasibility of plating without the use of corrosive etchants.

    20. Macrocycles 27: Cyclic aliphatic polyesters of isosorbide (pages 3414–3424)

      Hans R. Kricheldorf, Saber Chatti, Gert Schwarz and Ralf-P. Krüger

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10933

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      Isosorbide was polycondensed with aliphatic dicarboxylic acid dichloride and pyridine under various reaction conditions. Reactions of the resulting cyclic oligo- and polyesters with transesterification catalysts were examined.

    21. Synthesis of well-defined macromonomers and comb copolymers from polymers made by atom transfer radical polymerization (pages 3425–3439)

      Andreas Muehlebach and François Rime

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10940

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      Poly(n-butyl acrylate) macromonomers with predetermined molecular weights (1300 < number-average molecular weight < 23,000) and low polydispersity indices (≈1.1) were synthesized from bromine-terminated atom transfer radical polymerization polymers via end-group substitution with acrylic acid and methacrylic acid. These macromonomers, having a high degree of end-group functionalization (>90%), were radically homopolymerized and copolymerized to obtain comb (co)polymers. A high macromonomer concentration, combined with a low radical flux, was needed to obtain a high macromonomer conversion and a reasonable degree of polymerization. If N,N-dimethylaminoethyl methacrylate (DMAEMA) as a comonomer was used, simultaneous decreases in the macromonomer and DMAEMA concentrations and almost quantitative conversions of the macromonomers and comonomer were observed under optimized reaction conditions.

    22. Cationic photopolymerization of epoxynorbornane linseed oils: The effect of diluents (pages 3440–3456)

      Zhengang Zong, Mark D. Soucek, Yubiao Liu and Jun Hu

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10942

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      New epoxynorbornane linseed oils (ENLOs) were prepared as a function of the norbornene content. The cationic photopolymerization of ENLOs was investigated with real-time infrared spectroscopy and photo-differential scanning calorimetry. The effects of reactive and nonreactive diluents on the polymerization rate were studied. The relative reactivity of the oxiranes was not as important as the viscosity of the reacting system, and it was proposed that the cationic photopolymerization of ENLOs was controlled by diffusion.

    23. Graft copolymerization of butyl acrylate and 2-ethyl hexyl acrylate from labile chlorines of poly(vinyl chloride) by atom transfer radical polymerization (pages 3457–3462)

      Niyazi Bicak and Mesut Ozlem

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10944

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      Labile chlorines of poly(vinyl chloride) (PVC) served as initiation sites for the preparation of graft copolymers of PVC with butyl acrylate and 2-etylhexylacrylate by atom transfer radical polymerization.

  4. Rapid Communication

    1. Top of page
    2. Editorial
    3. Highlight
    4. Articles
    5. Rapid Communication
    1. Effect of hydrogen-bonding interaction on radical polymerization of di-n-butyl itaconate (pages 3463–3467)

      Tomohiro Hirano, Kousuke Higashi, Makiko Seno and Tsuneyuki Sato

      Version of Record online: 24 SEP 2003 | DOI: 10.1002/pola.10957

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      Radical polymerizations of di-n-butyl itaconate (DBI) were examined in the presence of amide compounds that could form a complex with DBI monomer via a hydrogen-bonding interaction. The use of amide compounds as solvents succeeded to suppress the intramolecular chain-transfer reaction significantly, whereas catalytic amounts of amide compounds were of little effect. It was also assumed that a hydrogen-bonding interaction plays an important role not only for suppression of the intramolecular chain-transfer reaction but for stereospecificity of polymerization. These results suggested that even a weak hydrogen-bonding interaction could be used for control of a radical polymerization reaction.