Journal of Polymer Science Part A: Polymer Chemistry

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

15 November 2002

Volume 40, Issue 22

Pages 3873–4116

  1. Articles

    1. Top of page
    2. Articles
    1. Effects of organophilic clay on the solvent-maintaining capability, dimensional stability, and electrochemical properties of gel poly(vinylidene fluoride) nanocomposite electrolytes (pages 3873–3882)

      H. J. Liu, J. J. Hwang and Y. W. Chen-Yang

      Version of Record online: 25 SEP 2002 | DOI: 10.1002/pola.10484

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      A series of gel poly(vinylidene fluoride) nanocomposite electrolyte materials were successfully prepared by the addition of the appropriate percentages of dimethylformamide or propylene carbonate/ethylene carbonate as a cosolvent, organophilic clay, and lithium perchlorate to poly(vinylidene fluoride). The maximum ionic conductivity was 1.03 × 10−2 S/cm, and the materials exhibited better film formation, solvent-maintaining capability, and dimensional stability than electrolyte films without added organophilic clays. The results of cyclic voltammetry testing showed that the addition of organophilic clays significantly enhanced the electrochemical stability of the polymer electrolyte system.

    2. Synthesis and crosslinking of polyethers that have mesogenic cores and propargyl groups (pages 3883–3892)

      J. Bonet, L. Callau, J. A. Reina, M. Galià and V. Cádiz

      Version of Record online: 25 SEP 2002 | DOI: 10.1002/pola.10453

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      We modified poly(epichlorohydrin) (PECH) with biphenyl carboxylic and naphthalene carboxylic acid derivatives which contains propargyloxy moieties. We obtained only one side chain liquid crystalline polymer. A smectic A mesophase of this biphenyl derivative was identified by DSC, light polarized optical microscopy and X-ray diffraction. Partially curing this reactive liquid crystalline polymer resulted in the formation of an anisotropic elastomer when the curing was radically initiated in the range of mesophase stability.

    3. Synthesis and crosslinking of vinyl-terminated biphenyl and naphthalene liquid-crystalline poly(epichlorohydrin) derivatives: Effect of nonmesogenic nonvinylic units on the mesogenic properties (pages 3893–3908)

      Lourdes Callau, José Antonio Reina and Ana Mantecón

      Version of Record online: 27 SEP 2002 | DOI: 10.1002/pola.10445

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      Two series of vinyl-terminated side-chain liquid-crystalline polyethers containing ethylene oxide or glycidyl aromatic carboxylates as spacers were synthesized. The mesogenic cores were 4,4′-biphenyl or 2,6-naphthalene moieties. The polymers were synthesized by chemically modifying poly(epichlorohydrin) or poly(epichlorohydrin)-poly(ethylene oxide). In most cases the degree of modification achieved was higher than 90%. The liquid-crystal behavior, shown by most polymers, was examined by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. Crosslinking of the polymers was done by peroxide-type initiators that led to liquid-crystal thermosets or elastomers.

    4. Synthesis of novel ladder polymers of poly(3,4-dihydro-2H-pyran-2-methanol) (pages 3909–3915)

      Magdy Youssef Abdelaal

      Version of Record online: 1 OCT 2002 | DOI: 10.1002/pola.10469

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      The polydispersity indices of cationic polydi(3,4-dihydro-2H-pyran-2-methyl) oxalate, adipate, and phthalate obtained at different temperatures have been determined. On the basis of the change in the polydispersity index accompanied by hydrolysis, oxalate-, adipate-, and phthalate-based polymers were concluded as ladder, semiladder, and intramolecular linked structures.

    5. Liquid-crystalline thermosets from mesogenic dimeric epoxy resins by tertiary amine catalysis (pages 3916–3926)

      D. Ribera, A. Mantecón and A. Serra

      Version of Record online: 1 OCT 2002 | DOI: 10.1002/pola.10457

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      Liquid-crystalline thermosets (LCTs) were prepared by the curing of difunctional liquid-crystalline dimeric epoxy monomers with mesogenic imines and central spacers of different lengths with tertiary amines as catalysts. The locked mesophases of the LCTs, characterized by polarized optical microscopy and wide-angle X-ray scattering, were smectic-C. The influence of a 7.1-T magnetic field on the macroscopic orientation of these materials was studied by dynamic mechanical analysis, and the order parameter was determined by IR dichroism.

    6. π-Conjugated oligomers containing tropone in the main chain: Synthesis, characterization, and optical properties (pages 3927–3937)

      Koji Takagi, Yukimi Nishikawa, Naomi Nishioka, Hideo Kunisada and Yasuo Yuki

      Version of Record online: 1 OCT 2002 | DOI: 10.1002/pola.10487

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      Tropone-containing π-conjugated oligomers were synthesized by Wittig polycondensation and were characterized by NMR, infrared, thermogravimetric analysis, ultraviolet–visible, and photoluminescence measurements. The influence of the tropone content and kind of aromatic ring was carefully investigated from the standpoint of the oligomers' optical properties, which were compared with those of model compounds corresponding to the repeating unit.

    7. Polymerization of vinyl ethers with transition-metal catalysts: An examination of the stereoregularity of the formed polymers (pages 3938–3943)

      Takaaki Kawaguchi, Fumio Sanda and Toshio Masuda

      Version of Record online: 1 OCT 2002 | DOI: 10.1002/pola.10483

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      The polymerization of isobutyl vinyl ether (IBVE) and tert-butyl vinyl ether (TBVE) was carried out with metallocene and nonmetallocene catalysts, and the stereoregularity of the formed polymers was examined with 13C NMR spectroscopy. IBVE afforded polymers with 63–68% dyad isotacticity by polymerization with mixtures of metallocene catalysts and methyl aluminoxane as a cocatalyst in toluene as a solvent. However, TBVE yielded polymers with 47–52% dyad isotacticity (21–28% triad isotacticity) under the same conditions, the isotacticity being lower than that of poly(isobutyl vinyl ether) (PIBVE). Nonmetallocene catalysts, including Ti, Zr, and Hf complexes with two phenoxy imine chelate ligands, provided PIBVE and poly(tert-butyl vinyl ether) with 63–68 and 45–51% dyad isotacticity, respectively.

    8. Correlation between the tacticity and content of labile nondefect structures in poly(vinyl chloride) (pages 3944–3949)

      Gerardo Martinez and Jose Luis Millan

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10474

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      The content of mm isotactic triads taking the GTTG conformation for samples of poly(vinyl chloride) (PVC) fractions of different tacticities was measured through a substitution reaction with sodium benzenethiolate. This quantity changed linearly with the ratio of rmmmrx to mmmmrx (x = m or r), as accurately determined by 13C NMR spectroscopy. In a comparison of this correlation and that obtained between the thermal degradation stability and overall isotactic content, as studied previously, some novel evidence for the GTTG conformation of a few mm triads, termini of isotactic sequences no shorter than one heptad as specific labile sites in PVC, was obtained.

    9. Melt grafting of N-carbamyl maleamic acid onto linear low-density polyethylene (pages 3950–3958)

      Andrés E. Ciolino, Marcelo D. Failla and Enrique M. Vallés

      Version of Record online: 4 OCT 2002 | DOI: 10.1002/pola.10478

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      Linear low-density polyethylene (PE) was functionalized in the melt with different concentrations of N-carbamyl maleamic acid (NCMA) and 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane as an initiator. The amount of acid incorporated into the PE chains increased with the concentration of both the NCMA and initiator. An analysis of Fourier transform infrared spectra indicated that the chemical structure of NCMA was altered during the modification process. The enthalpy of fusion of PE was not affected noticeably by the grafting of NCMA, whereas the melting temperature of PE decreased slightly after the modification. The modification promoted the crosslinking of molecules, as revealed by the rheological response of the molten polymer under dynamic shear flow. The values of both the viscosity and elastic modulus of the modified polymer were larger than the corresponding properties of the original PE.

    10. Synthesis and characterization of poly(benzobisthiazole)s derived from halogenated phthalic acid and isophthalic acid (pages 3959–3966)

      Roli Saxena, L. D. Kandpal and G. N. Mathur

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10481

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      Poly(benzobisthiazole)s containing tetrafluorophenyl and bromophenyl moieties were synthesized via the polycondensation of 2,5-diamino-1,4-benzenedithiol dihydrochloride with tetrafluorophthalic acid and 4-bromoisophthalic acid under a nitrogen atmosphere. The polymers were characterized by X-ray diffraction, spectroscopy (infrared and solid-state 13C NMR), and thermal analysis, including differential scanning calorimetry and thermogravimetric analysis. The thermogravimetric analysis showed that the thermal stability of the polymers was 490–515 °C under a nitrogen atmosphere. The synthesized polymers showed good solubility in organic solvents.

    11. Emulsion polymerization of divinyl monomers stabilized by sodium dodecyl sulfate and bis(2-ethylhexyl)sulfosuccinate sodium salt (pages 3967–3973)

      Barbara Gawdzik and Małgorzata Maciejewska

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10485

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      The emulsion polymerization of divinyl monomers in the presence of sodium dodecyl sulfate and bis(2-ethylhexyl)sulfosuccinate sodium salt as surfactants was prepared. The influence of monomer type and kind of surfactants on the particle size distribution is examined. Additionally, the porous structure of nanosphere aggregates obtained after emulsion breaking is investigated. The obtained aggregates have pores formed by free volumes between the packed particles.

    12. Dimethyldioxirane as a new and effective oxidation agent for the epoxidation of α,ω-di(isobutenyl)polyisobutylene: A convenient synthesis of α,ω-di(2-methyl-3-hydroxypropyl)-polyisobutylene (pages 3974–3986)

      Sándor Kéki, Miklós Nagy, György Deák, Albert Lévai and Miklós Zsuga

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10455

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      The synthesis and characterization of α,ω-di(2-methyl-2,3-epoxypropyl)polyisobutylene are reported. The epoxidation of α,ω-di(isobutenyl)polyisobutylene was achieved at room temperature with dimethyldioxirane, which proved to be a very effective reagent for epoxidation without the formation of byproducts. The epoxy end groups were converted quantitatively into aldehyde termini with zinc bromide as a catalyst. The aldehyde groups were then reduced with LiAlH4 into primary hydroxyl functions to obtain α,ω-di(2-methyl-3-hydroxylpropyl)polyisobutylene with high efficiency.

    13. Reaction kinetics and gel effect on the polymerization of 2-ethoxyethyl methacrylate and 2(2-ethoxyethoxy) ethyl methacrylate (pages 3987–4001)

      F. García, J. M. García, F. Rubio, J. L. de la Peña, J. Guzmán and E. Riande

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10480

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      The polymerizations kinetics at several temperatures of 2-ethoxyethyl methacrylate (EEMA) and 2-2(2-ethoxyethoxy)ethyl methacrylate (DEMA) in the bulk and in dioxane solutions are described. Ultraviolet Spectroscopy and Electron paramagnetic resonance spectroscopy techniques were used to study the polymerizations and to determine the values of the propagation kp and termination kt, rate constants.

    14. Effect of central spacer chain structure on cationic cyclopolymerization tendency of divinyl ethers (pages 4002–4012)

      Tamotsu Hashimoto, Minoru Ohashi and Toshiyuki Kodaira

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10486

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      To clarify the effects of the central spacer chain structure of divinyl ethers on their cationic cyclopolymerization tendency, 1,4-bis[(2-vinyloxy)ethoxy]benzene (1), 1,4-bis[(2-vinyloxy)ethoxy]butane (2), 1,6-bis[(2-vinyloxy)ethoxy]hexane (3), 1,8-bis[(2-vinyloxy)ethoxy]octane (4), and 1,4-bis[(4-vinyloxy)butoxy]butane (5) were polymerized with the hydrogen chloride/zinc chloride (HCl/ZnCl2) initiating system in methylene chloride (CH2Cl2) at 0 °C at low initial monomer concentration ([M]0 = 0.15 M). Among the divinyl ethers used, the order of cyclopolymerization tendency was 2∼3 > 4 > 1∼5. These results are discussed in terms of the structural variety of the spacer chains: (1) the presence of benzene ring (1 vs 2), (2) their length (2 vs 3 and 4), and (3) the position of ether oxygen (4 vs 5).

    15. Dehydrocoupling and Diels–Alder reactions on siloxane polymers (pages 4013–4019)

      Chungkyun Kim and Kyungran Kwark

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10494

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      Dehydrocoupling reactions between poly(methylhydrosiloxane) {Me3SiO–[MeSi(H)O]n–SiMe3} and alcohols were introduced under catalytically mild conditions. The degrees of conversion of Si[BOND]H bonds in polysiloxane were monitored with 1H NMR spectra. The reaction of the 9-methoxyanthracene adduct on siloxane polymers and maleimide derivatives led to [2+4]-cycloadducts in very high yields.

    16. Synthesis of π-conjugated oligomer that can form metallo polymers (pages 4020–4023)

      Abdelkrim El-Ghayoury, Albertus P. H. J. Schenning and E. W. Meijer

      Version of Record online: 2 OCT 2002 | DOI: 10.1002/pola.10477

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      An oligo(p-phenylene vinylene) that contains terpyridine ligands has been synthesized. Upon addition of metal ions, a π-conjugated metallo polymer is formed in which the well-defined character of oligomers and the material properties of polymers are combined.

    17. Investigation of polycondensation through the copolycondensation of preformed oligomers and bisphenols by a two-stage solution reaction with tosyl chloride, dimethylformamide, and pyridine (pages 4024–4031)

      Fukuji Higashi and Kanako Sugishita

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10491

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      A two-stage copolycondensation of an equimolar mixture of isophthalic acid and terephthalic acid first with a bisphenol (BP; M1) and then with another BP (M2) was studied to determine how comonomer M2 should react with preformed oligomers from M1 to lead to a high molecular weight. The results were significantly affected by a combination of BPs and were examined on the basis of the distribution of M2 in the resultant copolymers by 1H NMR.

    18. Reversible addition–fragmentation chain-transfer polymerization: Unambiguous end-group assignment via electrospray ionization mass spectrometry (pages 4032–4037)

      Philipp Vana, Luca Albertin, Leonie Barner, Thomas P. Davis and Christopher Barner-Kowollik

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10500

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      Electrospray ionization mass spectrometry was performed to identify the structure of polymeric methyl acrylates generated via the cumyl dithiobenzoate (CDB), cumyl p-fluorodithiobenzoate (CPFDB), and 1-phenylethyl dithiobenzoate (PEDB) mediated reversible addition–fragmentation chain-transfer (RAFT) polymerizations. The relatively simple spectra clearly demonstrate the end groups of this living free-radical polymerization technique. Only polymeric chains carrying one leaving group of the RAFT agent and the dithiobenzoate end group as the active RAFT center were discovered.

    19. Synthesis of optically active alicyclic polyimides from a chiral, nonracemic dianhydride (pages 4038–4044)

      Kazuaki Kudo, Daigo Nonokawa, Jun Li and Shinsaku Shiraishi

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10497

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      Optically active alicyclic polyimides were prepared from (−)-[1S*,5R*,6S*]-3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3′-(tetrahydrofuran-2′,5′-dione) [(−)-DAn] and aromatic diamines by a two-step procedure. The chiral dianhydride (−)-DAn was synthesized through an asymmetric Diels–Alder reaction of an itaconic acid derivative as a key step. The polyimides were film-formable, thermally stable, and highly soluble toward polar organic solvents. The circular dichroism spectra of the chiral polyimides indicated that they had a higher order structure to some extent in solution.

    20. Photobase generation from amineimide derivatives and their use for curing an epoxide/thiol system (pages 4045–4052)

      Shigeki Katogi and Masami Yusa

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10489

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      The photobase generation from a series of amineimide derivatives is investigated. The results of gas chromatographic-mass spectrometric analysis and the pH changes indicated that amineimide derivatives produce base via photolysis. The conversion of the photolysis depends on the functional group introduced, that is, NO2 > N(CH3)2 > CN > OCH3 > H. It was confirmed that by adding aminimide derivatives with NO2 and N(CH3)2 groups, the curing of an epoxide/thiol system is shifted to lower temperature after UV irradiation.

    21. Synthesis of polyacetals with various main-chain structures by the self-polyaddition of vinyl ethers with a hydroxyl function (pages 4053–4064)

      Tamotsu Hashimoto, Koji Ishizuka, Akihiro Umehara and Toshiyuki Kodaira

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10490

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      To establish the optimum conditions for obtaining high molecular weight polyacetals by the self-polyaddition of vinyl ethers with a hydroxyl group, we performed the polymerization of 4-hydroxybutyl vinyl ether (CH2[DOUBLE BOND]CH[BOND]O[BOND]CH2CH2CH2CH2[BOND]OH) with various acidic catalysts [p-toluene sulfonic acid monohydrate, p-toluene sulfonic anhydride (TSAA), pyridinium p-toluene sulfonate, HCl, and BF3OEt2] in different solvents (tetrahydrofuran and toluene) at 0 °C. The reaction with TSAA in tetrahydrofuran led to the highest molecular weight polymers (number-average molecular weight = 110,000, weight-average molecular weight/number-average molecular weight = 1.59). 2-Hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, and tricyclodecane dimethanol monovinyl ether were also employed as monomers, and new polyacetals with various main-chain structures were synthesized.

    22. Effect of the sulfonic acid group on copolymers of aniline and toluidine with m-aminobenzene sulfonic acid (pages 4065–4076)

      Palle Swapna Rao and D. N. Sathyanarayana

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10495

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      Inverse emulsion polymerization with benzoyl peroxide as an oxidant has been employed in the preparation of self-doped conducting polymers of aniline and toluidine with m-aminobenzene sulfonic acid with relatively higher electrical conductivity and high yields. Spectroscopic, morphological, and electrical conductivity studies have provided insight into the structural and electronic properties of the copolymers. The differences in the properties of polyaniline and polytoluidine due to the sulfonic acid ring substituent on the phenyl ring are discussed. The steric effect of the [BOND]SO2OH groups causes a loss of coplanarity in the π system, which results in decreased conjugation. The scanning electron micrographs of the copolymers reveal regions of sharp-edged, needle-shaped structures, whereas the X-ray diffraction patterns show that the copolymers are relatively more crystalline in nature.

    23. Preparation and characterization of N-methyl-substituted polyurethane (pages 4077–4083)

      Hee-Sung Choi and Si-Tae Noh

      Version of Record online: 3 OCT 2002 | DOI: 10.1002/pola.10492

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      We prepared N-methyl-substituted polyurethanes with different substitution degrees from sodium hydride, methyl p-toluene sulfonate, and polyether–polyurethane containing poly(oxytetramethylene) glycol, 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol. The chemical structures were characterized with Fourier transform infrared and 1H NMR. To investigate the effects of the N-substitution degree on the morphology, thermal stability, and mechanical properties, we used differential scanning calorimetry, thermogravimetric analysis, and a universal testing machine.

    24. Low dielectric thermoset. II. Synthesis and properties of novel 2,6-dimethyl phenol–dipentene epoxy (pages 4084–4097)

      Ching Hsuan Lin, Zheng Rong Jiang and Chun Shan Wang

      Version of Record online: 4 OCT 2002 | DOI: 10.1002/pola.10488

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      A 2,6-dimethyl phenol–dipentene adduct was synthesized from dipentene (DP) and 2,6-dimethyl phenol, and then a 2,6-dimethyl phenol–DP epoxy was synthesized from the reaction of the resultant 2,6-dimethyl phenol–DP adduct and epichlorohydrin. The cured 2,6-dimethyl phenol–DP epoxy exhibited a lower dielectric constant (ca. 3.1), a lower dissipation factor (ca. 0.065), a lower modulus, lower thermal stability (5% degradation temperature = 366–424 °C), and lower moisture absorption (1.21–2.18%) than the bisphenol A system but a higher glass-transition temperature (ca. 173–222 °C).

    25. Epoxy-functionalized, low-glass-transition-temperature latex. II. Interdiffusion versus crosslinking in the presence of a diamine (pages 4098–4116)

      Frédéric Tronc, Warner Chen, Mitchell A. Winnik, Sarah T. Eckersley, Gene D. Rose, J. M. Weishuhn and D. M. Meunier

      Version of Record online: 4 OCT 2002 | DOI: 10.1002/pola.10462

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      This article examines the competition between the polymer diffusion rate and the crosslinking rate in low-Tg epoxy-containing latex films in the presence of diamine. The films were formed from a mixture of donor- and acceptor-labeled poly(butyl acrylate-co-methyl methacrylate-co-glycidyl methacrylate) copolymer latex. We studied the influence of several parameters upon the growth rate of gel content and the rate of polymer diffusion. These factors include the molecular weight of the latex polymer, the presence or absence of a diamine crosslinking agent, and the cure protocol. The results were compared to the predictions of a recent theory of the competition between crosslinking and polymer diffusion across interfaces.