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  • 1995-1999  (17,320)
  • 1985-1989  (20,502)
  • Polymer and Materials Science  (31,432)
  • Chemical Engineering  (5,177)
  • Genetics  (1,213)
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  • 101
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of new aromatic polyesters and a polyether derived from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2229-2235 
    Details
    ISSN: 0887-624X
    Keywords: polyarylates ; aromatic polyether ; 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polyarylates having benzopinacolone units were synthesized from 2,2-bis(4-hydroxyphenyl)-1,2-diphenylethanone and aromatic dicarboxylic acid chlorides. The polymers having an inherent viscosity of 0.71-0.94 dL/g were obtained by the two-phase method using toluene as an organic solvent. The polymers were easily soluble in various organic solvents and had high glass transition temperatures in the range of 200-240°C. An aromatic polyether having benzopinacolone unit was also prepared. However, its inherent viscosity was low because of the occurrence of a side reaction. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2229-2235, 1998
    Additional Material: 2 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    New polymer syntheses. XC. A-B-A triblock copolymers with hyperbranched polyester A-blocks (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 31-38 
    Details
    ISSN: 0887-624X
    Keywords: triblock copolymers ; polycondensations ; telechelic character ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Telechelic oligo(ether-ketone)s containing two trimethylsiloxy end groups and one methyl group per repeating unit were prepared by polycondensation of 4-fluoro-2′-methyl-4′-(trimethylsiloxy)benzophenone. The telechelic character was achieved by cocondensation of a small amount of silylated bisphenol-P. The end groups of the silylated oligo(ether-ketone)s were acetylated by means of acetyl chloride. On the basis of 1H-NMR end group analyses two samples of α,ω-bis(acetoxy) oligo(ether-ketone)s with DP = 14 and DP ∼ 28 were obtained. These oligo(ether-ketone)s and a 70 or 140 fold molar amount of silylated 3,5-bis(acetoxy)benzoic acid were polycondensed at 270°C in bulk. The resulting A-B-A triblock copolymers were fractionated by dissolution in tetrahydrofuran. In three out of four experiments a small fraction of precipitated material rich in oligo(ether-ketone) was isolated. The purified triblock copolymers were characterized by inherent viscosities and NMR spectra. For those samples containing the long oligo(ether-ketone) block a low degree of crystallinity was observed after annealing. Four additional polycondensations were conducted with an initial reaction temperature of 290°C. In this way a completely soluble and amorphous triblock copolymer was obtained. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 31-38, 1998
    Additional Material: 8 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    Liquid crystalline epoxy resins by polyaddition of diglycidyl ether of 4,4′-dihydroxybiphenyl and difunctional aromatic compounds (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 21-29 
    Details
    ISSN: 0887-624X
    Keywords: liquid crystalline polymers ; epoxy resins ; thermotropic ; polymer chain extension ; catalytic polyaddition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work is a continuation of the authors' earlier investigations of liquid crystalline epoxy resins prepared from diglycidyl ether of 4,4′-dihydroxybiphenyl (DGE-DHBP), which was used as a mesogenic agent, and aliphatic dicarboxylic compounds, which were used as flexible spacers. In this paper, the synthesis and characterization of liquid crystalline epoxy resins, prepared from DGE-DHBP and difunctional aromatic compounds are described. Three series of liquid crystalline epoxy resins were prepared by chain extension of DGE-DHBP with isomeric hydroxybenzoic and benzenedicarboxylic acids as well as diphenols. An isophthalic-terminated polyether was applied to decrease the temperature of phase transitions. The syntheses were carried out by catalytic polyaddition in the melt. Triphenylphosphine was applied as the catalyst. The resulting epoxy resins were investigated by DSC, polarizing microscope as well as by X-ray and IR spectroscopy. The phase transition temperatures and the type of mesophase of the resulting products depend on the character of the functional groups in the chain extender and on the position of the functional groups in the aromatic ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 21-29, 1998
    Additional Material: 4 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    Synthesis and properties of new soluble aromatic polybenzoxazoles from 4,4′-diamino-3,3′-dihydroxytriphenylamines and aromatic dicarboxylic acids (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1987-1994 
    Details
    ISSN: 0887-624X
    Keywords: triphenylamine-based bis(o-aminophenol)s ; aromatic polybenzoxazoles ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new triphenylamine-based bis (o-aminophenol) monomers, 4,4′-diamino-3,3′-dihydroxytriphenylamines, were successfully synthesized by the cesium fluoride-mediated condensation of 2-(benzyloxy)-4-fluoronitrobenzene with aniline derivatives, followed by simultaneous deprotection and reduction. Aromatic polybenzoxazoles having inherent viscosities of 0.58-1.05 dL/g were obtained by the low-temperature solution polycondensation of the bis(aminophenol)s with various aromatic dicarboxylic acid chlorides and the subsequent thermal cyclodehydration of the resultant poly(hydroxyamide)s. All the polybenzoxazoles were amorphous, and most of them were soluble in organic solvents such as m-cresol and o-chlorophenol. Flexible and tough films of polybenzoxazoles could be cast from the DMAc solutions of some aromatic poly(hydroxyamide)s, followed by thermal cyclodehydration. The glass transition temperatures and 10% weight loss temperatures of the polybenzoxazoles under nitrogen were in the range of 262-327 and 610-640°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1987-1994, 1998
    Additional Material: 1 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    Asymmetric anionic polymerization of (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl)methyl methacrylate leading to a helical polymer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2013-2019 
    Details
    ISSN: 0887-624X
    Keywords: asymmetric polymerization ; anionic polymerization ; (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl) methyl methacrylate ; optically active polymer ; helix ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel racemic methacrylate, (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl)-methyl methacrylate1 (2F4F2PyMA), was synthesized and polymerized with chiral complexes of N,N′-diphenylethylenediamine monolithium amide (DPEDA-Li) with (-)-sparteine (Sp), (2S, 3S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB), and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP) in toluene at -78°C. The monomer showed higher resistance against methanolysis compared with triphenylmethyl methacrylate (TrMA) and several other analogues. In the asymmetric anionic polymerization of 2F4F2PyMA, PMP was found to be a more effective chiral ligand than DDB and Sp and gave quantitatively an optically active polymer with nearly perfect isotacticity. Enantiomer selection was observed in the polymerization of racemic 2F4F2PyMA with the chiral lithium complexes. Chiral recognition ability of the optically active poly(2F4F2PyMA) was examined by an enantioselective adsorption experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2013-2019, 1998
    Additional Material: 4 Ill.
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  • 106
    Electronic Resource
    Electronic Resource
    Characterization and degradation of the poly(methylphenylsiloxane)-poly(methyl methacrylate) graft copolymer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2521-2530 
    Details
    ISSN: 0887-624X
    Keywords: poly(methylphenylsiloxane) ; poly(methyl methacrylate) ; graft copolymer ; spin-spin relaxation ; degradation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(methylphenylsiloxane)-poly(methyl methacrylate) graft copolymers (PSXE-g-PMMA) were prepared by condensation reaction of poly(methylphenylsiloxane)-containing epoxy resin (PSXE) with carboxyl-terminated poly(methyl methacrylate) (PMMA), and they were characterized by gel permeation chromatography (GPC), infrared (IR), and 29Si and 13C nuclear magnetic resonance (NMR). The microstructure of the PSXE-g-PMMA graft copolymer was investigated by proton spin-spin relaxation T2 measurements. The thermal stability and apparent activation energy for thermal degradation of these copolymers were studied by thermogravimetry and compared with unmodified PMMA. The incorporation of poly(methylphenylsiloxane) segments in graft copolymers improved thermal stability of PMMA and enhanced the activation energy for thermal degradation of PMMA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2521-2530, 1998
    Additional Material: 11 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    Amine-linked thioxanthones as water-compatible photoinitiators (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2563-2570 
    Details
    ISSN: 0887-624X
    Keywords: thioxanthone derivatives ; water-compatible photoinitiator ; absorption spectrum ; fluorescence ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six amine-linked thioxanthones, i.e., 2-(2-hydroxy-3-[bis(2-hydroxyethyl)amino]propoxy)thioxanthone (HAPTX) and its 4-methyl, 1,3-dimethyl, 1,4-dimethyl, 3,4-dimethyl, and 1,3,4-trimethyl substituted derivatives, were synthesized as water-compatible photoinitiators and identified with FTIR, MS, NMR, and elementary analysis. The absorption and fluorescence properties were studied. Their photoinitiating polymerization efficiencies were tested with a recording dilatometer utilizing acrylamide as monomer in aqueous solution. The results show that the six amine-linked thioxanthones can independently initiate acrylamide polymerization efficiently without additional external amines as co-initiators. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2563-2570, 1998
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  • 108
    Electronic Resource
    Electronic Resource
    Oxidative polymerization of phenylenediamines catalyzed by horseradish peroxidase (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2593-2600 
    Details
    ISSN: 0887-624X
    Keywords: phenylenediamine ; oxidative polymerization ; enzyme ; horseradish peroxidase ; CD spectrum ; organic solvent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ortho-, meta-, and para-phenylenediamines were polymerized using hydrogen peroxide as an oxidant and horseradish peroxidase as a catalyst in mixed solvents of 1,4-dioxane and water. The yield of the polymers was strongly dependent on solvent composition, and maximum yields were obtained at 15-30% 1,4-dioxane. The analysis of circular dichroic spectra of the enzyme suggested that enzyme structure was significantly modified at high 1,4-dioxane contents, which may be responsible for the decrease of catalytic activity of the enzyme. On the basis of IR and electronic spectra of the polymers, it was considered that o- and p-phenylenediamine polymers retain disubstituted benzene nuclei, which suggests that the polymerization proceeded mainly via N - N coupling. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2593-2600, 1998
    Additional Material: 6 Ill.
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  • 109
    Electronic Resource
    Electronic Resource
    Synthesis of alkoxyamine initiators for controlled radical polymerization (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2667-2668 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 110
    Electronic Resource
    Electronic Resource
    Syntheses and properties of liquid crystalline N-substituted pyrroles and their polymers (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2691-2698 
    Details
    ISSN: 0887-624X
    Keywords: N-substituted pyrrole ; liquid crystalline polymer ; polypyrrole ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three liquid crystalline N-substituted pyrroles were synthesized from 6-(1-pyrrolyl)hexanol with phenolic derivatives having a mesogenic core of cyclohexylbenzene or biphenyl by Mitsunobu reaction. These pyrroles had two anodic peaks at 1.4 and 1.8 V (vs. SCE). The former was due to an oxidation of the pyrrole moiety and the latter was due to an oxidation of the mesogenic moiety. These pyrrole monomers were polymerized by electrochemical and chemical methods. The potentiostatic method and the chemical method using FeCl3 gave a soluble and fusible polymer, respectively. A polymer having a mesogenic core of cyclohexyl benzene obtained by the chemical method and a polymer having a mesogenic core of biphenylketone obtained by the potentiostatic method had a liquid-crystalline phase. The phase was identified as smectic A by polarizing microscopy and XRD analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2691-2698, 1998
    Additional Material: 5 Ill.
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  • 111
    Electronic Resource
    Electronic Resource
    Polymerization of acrylamide in the presence of ultrasound and peroxomonosulfate (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2715-2719 
    Details
    ISSN: 0887-624X
    Keywords: polymerization ; acrylamide ; peroxomonosulfate ; ultrasound ; mechanism ; rate parameters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of acrylamide (M) in the presence of ultrasound and peroxomonosulfate (PMS) was carried out for the first time for various concentration ranges of monomer and initiator and various temperatures at a constant frequency of 1 Mhz. The rate of polymerization Rp was found to increase with increase in the concentration of monomer and initiator and found to depend on [M] and [PMS]1/2. The rate of disappearance of initiator (-d[PMS]/dt) was also followed simultaneously under the experimental conditions and found to increase linearly with increase in [PMS]. A probable reaction mechanism was proposed on the basis of the observed results, and the individual rate constant were evaluated. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2715-2719, 1998
    Additional Material: 3 Ill.
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  • 112
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of chiral polyamides derived from glycine and (S)-5-amino-4-methoxypentanoic acid (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2741-2748 
    Details
    ISSN: 0887-624X
    Keywords: stereoregular polymers ; chiral polyamides ; ω-amino acids ; glycine ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoregular, enantiomerically pure, chiral polyamides of the -AB- type, containing a natural (glycine) and a synthetic [(S)-5-amino-4-methoxypentanoic acid (AMP)] component have been prepared by the active ester polycondensation method. Thus, polyamide 7 was obtained by polycondensation of the conveniently activated H2NGly-AMPCO2R unit (6). In this reaction, 7 appeared accompanied by a considerable amount of cyclic (Gly-AMP)2 (8), which makes the isolation and purification of 7 difficult. The formation of cyclic byproducts could be avoided by preparing and polymerizing the oligoamide H2NGly-AMP-AMPCO2R (11), which has the terminal carboxyl group activated as the pentachlorophenyl ester. The resulting polyamide (12) was obtained in 85% yield and free of macrolactams, such as 8. The new polyamides 7 and 12 were characterized by elemental analysis and infrared and 1H- and 13C-nuclear magnetic resonance spectroscopies. Thermal studies revealed that 12 is crystalline and yields films with spherulitic texture by slow evaporation of formic acid solutions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2741-2748, 1998
    Additional Material: 2 Ill.
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  • 113
    Electronic Resource
    Electronic Resource
    Mechanisms of thermal degradation of polystyrene, polymethacrylonitrile, and their copolymers on flash pyrolysis (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2315-2330 
    Details
    ISSN: 0887-624X
    Keywords: thermal degradation mechanism ; poly(styrene-co-methacrylonitrile) ; pyrolysis gas chromatography ; back-biting reaction ; depolymerization ; boundary effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of thermal degradation of homopolymers of styrene (St) and methacrylonitrile (MAN) and their copolymers was investigated theoretically and experimentally by the pyrolysis gas chromatography using a Curie-point pyrolyzer. Poly(St-co-MAN)s generate dimers and trimers as well as monomers by flash pyrolysis. Parameter α was proposed to account for the competition between the back-biting reaction and depolymerization. The back-biting parameter α is defined as the ratio of rate constants, α = kbb/kdp, where kbb is the rate constant for the back-biting reaction and kdp is that for depolymerization. The back-biting process is followed by β-scission, where dimer and trimer are generated, and directly correlated with the C - H bond dissociation energies in the polymer chain. Using the back-biting parameter α, where 1/α is equal to the zip length n in depolymerization, the boundary effect for the difference of monomer yields from the homopolymers of St and MAN and their copolymers is well explained. The calculated values of boundary effect parameters, βSt and βMAN, agreed well with the experimental results. It was found that thermal degradation mechanisms of homo- and copolymers of vinyl compounds can be analyzed comprehensively using the back-biting parameter α and the boundary effect parameter β. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2315-2330, 1998
    Additional Material: 10 Ill.
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  • 114
    Electronic Resource
    Electronic Resource
    New polymer syntheses XCIII. Hyperbranched homo- and copolyesters derived from gallic acid and β-(4-hydroxyphenyl)-propionic acid (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2347-2357 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hyperbranched homopolyester of gallic acid (GA) was prepared by polycondensation of acetylated gallic acid in bulk. Copolyesters of gallic acid and 3-hydroxybenzoic acid (3-HBA) or β-(4-hydroxyphenyl)propionic acid (HPPA) were prepared via the silylated monomers. The degree of branching was varied in both series via the molar fraction of gallic acid. A model reaction with silylated 4-methoxybenzoic acid suggests that all three acetoxy groups of gallic acid can react by ester interchange reactions under the chosen reaction conditions. Furthermore, highly branched copolyesters derived from equimolar ratios of HPPA and 2-, 3-, or 4-hydroxybenzoic acid, vanillic acid, or 4-hydroxycinnamic acid were synthesized. All these copolyesters were found to be amorphous with glass transition temperatures (Tg's) far below that of the hyperbranched poly(gallic acid). © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2347-2357, 1998
    Additional Material: 8 Ill.
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  • 115
    Electronic Resource
    Electronic Resource
    Epoxidation of bacterial polyesters with unsaturated side chains. II. Rate of epoxidation and polymer properties (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2381-2387 
    Details
    ISSN: 0887-624X
    Keywords: bacterial polyesters ; epoxidation of polyesters ; polyhydroxyalkanoates ; crosslinking polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(3-hydroxyoctanoate-co-3-hydroxy-10-undecenoate)s (PHOUs) with controlled amounts of unsaturated repeating units were epoxidized to various extents with m-chloroperbenzoic acid (MCPBA) in homogeneous solution. The epoxidation reaction was second order, with an initial rate constant of 1.1 × 10-3Lmol-1.s-1 at 20°C, regardless of the unsaturated unit content in PHOU. No substantial change in either molecular weight or molecular weight distribution occurred as a result of epoxidation, but the melt transition temperature and enthalpy of melting both decreased as the unsaturated groups were increasingly converted into epoxide groups. In contrast, the glass transition temperature (Tg) increased by approximately 0.25°C for each 1 mol % of epoxidation, irrespective of the composition of the PHOU. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2381-2387, 1998
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  • 116
    Electronic Resource
    Electronic Resource
    Sucrose-based epoxy monomers and their reactions with diethylenetriamine (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2397-2413 
    Details
    ISSN: 0887-624X
    Keywords: epoxy allyl sucroses ; epoxy crotyl sucroses ; sucrose-based epoxy monomers ; thermosets ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two sets of sucrose-based epoxy monomers, namely, epoxy allyl sucroses (EAS), and epoxy crotyl sucroses (ECS), were prepared by epoxidation of octa-O-allyl and octa-O-crotyl sucroses (OAS and OCS, respectively). Synthetic and structural characterization studies showed that the new epoxy monomers were mixtures of structural isomers and diastereoisomers that contained varying numbers of epoxy groups per sucrose. EAS and ECS can be tailored to contain an average of one to eight epoxy groups per sucrose. Quantitative 13C-NMR spectrometry and titrimetry were used independently to confirm the average number of epoxy groups per sucrose. Sucrose-based epoxy monomers were cured with diethylenetriamine (DETA) in a differential scanning calorimeter (DSC), and their curing characteristics were compared with those of diglycidyl ether of bisphenol A (DGEBA) and diepoxycrotyl ether of bisphenol A (DECEBA). EAS and DGEBA cured at 100 to 125°C and exhibited a heat of cure of about 108.8 kJ per mol epoxy. ECS and DECEBA cured at 150 and 171°C, respectively, and exhibited a heat of cure of about 83.7 kJ per mol epoxy. Depending upon the degree of epoxidation (average number of epoxy groups per sucrose) and the concentration of DETA, glass transition temperatures (Tgs) of cured EAS varied from -17 to 72°C. DETA-cured ECS containing an average of 7.3 epoxy groups per sucrose (ECS-7.3) showed no DSC glass transition between -140 and 220°C when the ratio of amine (NH) to epoxy group was 1:1 and 1.5:1. Maximum Tgs obtained for DETA-cured DGEBA and DECEBA polymers were 134 and 106°C, respectively. DETA-cured bisphenol A-based epoxy polymers degraded at about 340°C, as observed by thermogravimetric analysis (TGA). DETA-cured sucrose-based epoxy polymers degraded at about 320°C. Sucrose-based epoxies cured with DETA were found to bind aluminum, glass, and steel. Comparative lap shear tests (ASTM D1002-94) showed that DETA-cured epoxy allyl sucroses with an average of 3.2 epoxy groups per sucrose (EAS-3.2) generated a flexible adhesive comparable in bond strength to DGEBA. However, DETA-cured ECS-7.3 outperformed the bonding characteristics of both DGEBA and EAS-3.2. All sucrose-based epoxy polymers were crosslinked and insoluble in water, N,N-dimethylformamide, tetrahydrofuran, acetone, and dichloromethane. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2397-2413, 1998
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  • 117
    Electronic Resource
    Electronic Resource
    Block copolymers of telechelic poly(phenylene sulfide) and semiaromatic thermotropic liquid crystalline polyester segments (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2707-2713 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the synthesis and characterization of copolymers comprising poly(phenyl sulfide) (PPS) blocks and semiaromatic thermotropic liquid crystalline polymer (TLCP) blocks. The copolymers, synthesized by melt-transesterification of dicarboxy-terminated poly(phenylene sulfide) with poly(ethylene terephthalate-co-oxybenzoate) (PET/OB), were characterized using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized light optical microscopy (PLOM). The crystallizability and liquid crystalline properties of the copolymers are greatly influenced by the extent of interchange reactions, the mole percent of oxybenzoate with respect to the PET, the PPS : PET/OB weight ratio, and the reaction time. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2707-2713, 1998
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  • 118
    Electronic Resource
    Electronic Resource
    Polymerization of diphenylacetylenes having very bulky silyl groups and polymer properties (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2721-2725 
    Details
    ISSN: 0887-624X
    Keywords: poly(diphenylacetylene) ; tantalum catalyst ; metathesis polymerization ; thermal stability ; gas permeability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization and polymer properties of 1-phenyl-2-[4-(triphenylsilyl)phenyl]acetylene (pPh3SiDPA) and 1-phenyl-2-[4-(triisopropylsilyl)phenyl]acetylene (piPr3SiDPA), which have very bulky silyl groups, were examined. These monomers polymerized in good yields in the presence of TaCl5-based catalysts. The highest weight-average molecular weights of poly(pPh3SiDPA) and poly(piPr3SiDPA) reached about 1 × 106 and 4.8 × 106, respectively. The polymers were yellow to orange-colored solids which were soluble in toluene, chloroform, etc., and provided free-standing films by solution casting. The onset temperatures of weight loss of poly(pPh3SiDPA) and poly(piPr3SiDPA) in TGA in air were 430 and 270°C, respectively. The oxygen permeability coefficients of poly(pPh3SiDPA) and poly(piPr3SiDPA) at 25°C were 3.8 and 20 barrers, respectively, and relatively small. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2721-2725, 1998
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    Free radical dispersion polymerization of styrene in a mixture of 2-propanol and tetrahydrofuran (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2757-2761 
    Details
    ISSN: 0887-624X
    Keywords: free radical polymerization ; high-conversion model ; solvent effect ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radical dispersion polymerization of styrene in a mixture of 2-propanol and tetrahydrofuran was carried out at 70°C up to high conversions. The influence of the change of the critical chain length on the evolution of the insoluble polymer component was examined. Monomer conversion and the formation of the insoluble polymer component were measured in order to test a mathematical model presented in our previous article. The critical polymer chain length i0, the initiation rate constant kd, and the ratio kp/kt1/2, where kp and kt are propagation and termination rate constants, respectively, have been obtained and compared with those reported in the literature. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2757-2761, 1998
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    Synthesis and electrical-magnetic properties of polyaniline composites (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2799-2805 
    Details
    ISSN: 0887-624X
    Keywords: polyaniline (PANI) ; electrical-magnetic properties ; emeraldine base (EB) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Composites of polyaniline (PANI) with both conducting and ferromagnetic feature were synthesized by an improved method proposed by the authors. The electrical and ferromagnetic properties of the composites were measured as a function of the concentration of KOH solution used during polymerization. The conductivity of the composites at room temperature decreases with the increase of the concentration of KOH; the maximum conductivity of 8.0 × 10-1 S/cm can be obtained when 25 wt % of concentration of KOH was used. For a high concentration of KOH, ferromagnetic properties of the composites including a high saturated magnetization (∼ 10.0 emu/g) depending on the concentration of KOH solution and a lower coercive force (Hc ≈ 0) independent of the concentration of KOH solution were observed. It has been demonstrated that magnetic particles (Fe3O4) with nanometer size in the composites can be attributed to the ferromagnetic properties of the composites observed. For a lower concentration of KOH solution, on the other hand, the magnetic properties of the composites can be decomposed to Curie susceptibility χc depending on the temperature and Pauli susceptibility χP independent of the temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2799-2805, 1998
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    New hydrocarbon side chain liquid crystalline polysiloxane polymers: Synthesis, characterization, and thermotropic behavior (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2849-2863 
    Details
    ISSN: 0887-624X
    Keywords: liquid crystals ; all hydrocarbon ; side chain ; polysiloxane polymers ; smectic B phase ; smectic E phase ; X-ray diffraction ; spin-lattice relaxation time ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new and high-purity hydrocarbon liquid crystal monomers were synthesized through the acylation reaction, deoxygenation reaction, and Grignard reaction. 1H-NMR spectra and elemental analyses were used to examine their purity. The liquid crystalline polysiloxane polymers were obtained by grafting the monomers onto poly(methylhydrosiloxane). The thermal transition temperature, mesomorphic properties, and mesophase textures of the monomers and the polymers were determined by differential scanning calorimetry (dsc), polarized optical microscopy, and X-ray diffraction analysis. Moreover, we observed the even-odd effect of the smectic/isotropic transition temperature with the length variation of the substituents. In this study, we found by X-ray diffraction that the liquid crystalline polysiloxane polymers undergo a transition from smectic B to smectic E mesophase. However, dsc has difficulty detecting the phase transition process. By considering the spin-lattice relaxation time (T1), we can systematically explain the relation between the flexibility of the substituent with the smectic/isotropic transition temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2849-2863, 1998
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    Determination of chain transfer constant to dodecanethiol in styrene/methyl methacrylate and butyl acrylate/methyl methacrylate copolymerization and effect of chain length on composition and stereochemical configuration of copolymers (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2913-2925 
    Details
    ISSN: 0887-624X
    Keywords: dodecanethiol ; styrene-methyl methacrylate ; butyl acrylate-methyl methacrylate ; chain transfer constants ; stereochemical configuration ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radical copolymerization of styrene/methyl methacrylate (S/MMA) and butyl acrylate/methyl methacrylate (BA/MMA) in the presence of n-dodecanthiol (DDT) has been studied at 60°C in a 3 mol/L benzene solution using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. Overall chain transfer constant to DDT has been determined for both copolymerization systems, as a function of monomer feed composition using complete molecular weight distribution and the Mayo method. Overall transfer coefficients have values which are dependent on both monomer feed composition and individual comonomer transfer values. Composition, sequence distribution, and stereoregularity of copolymers obtained are, in our experimental conditions, independent of copolymer molecular weight. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2913-2925, 1998
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    Spontaneous alternating copolymerization of N-phenylmaleimide with ethyl α-phenylacrylate (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2927-2931 
    Details
    ISSN: 0887-624X
    Keywords: N-phenylmaleimide ; ethyl α-phenylacrylate ; alternating copolymer ; contact-charge transfer complex ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spontaneous copolymerization of N-phenylmaleimide (NPMI) (M1) with ethyl α-phenylacrylate (EPA)(M2) were carried out in dioxane at 85°C. A high alternating tendency was observed. The monomer reactivity ratios were r1 = 0.07 ±0.01 and r2 = 0.09 ± 0.02. The maximum copolymerization rate and molecular weight occurs at 70-80 mol% (M1) in feed ratio. The spontaneous alternating copolymerization is considered to be carried out via a contact-type charge transfer complex (CTC) formed between the monomers. Thermogravimetric analyses (TGA) indicate the resulting copolymers have high thermal stability. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2927-2931, 1998
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    Synthesis and characterization of biodegradable poly(L-aspartic acid-co-PEG) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2949-2959 
    Details
    ISSN: 0887-624X
    Keywords: aspartic acid anhydride ; poly(ethylene glycol) ; poly(L-aspartic acid-co-PEG) ; biodegradable polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The melt polycondensation reaction of the prepolymer prepared from N-(benzyloxycarbonyl)-L-aspartic acid anhydride (N-CBz-L-aspartic acid anhydride) and low molecular weight poly(ethylene glycol) (PEG) using titanium isopropoxide (TIP) as a catalyst produced the new biodegradable poly(L-aspartic acid-co-PEG). This new copolymer had pendant amine functional groups along the polymer backbone chain. The optimal reaction conditions for the preparation of the prepolymer were obtained by using a 0.12 mol % of p-toluenesulfonic acid with PEG 200 for 48 h. The weight-average molecular weight of the prepolymer increased from 1,290 to 31,700 upon melt polycondensation for 6 h at 130°C under vacuum using 0.5 wt % TIP as a catalyst. The synthesized monomer, prepolymer, and copolymer were characterized by FTIR, 1H- and 13C-NMR, and UV spectrophotometers. Thermal properties of the prepolymer and the protected copolymer were measured by DSC. The glass transition temperature (Tg) of the prepolymer shifted to a significantly higher temperature with increasing molecular weight via melt polycondensation reaction, and no melting temperature was observed. The in vitro hydrolytic degradation of these poly(L-aspartic acid-co-PEG) was measured in terms of molecular weight loss at different times and pHs at 37°C. This pH-dependent molecular weight loss was due to a simple hydrolysis of the backbone ester linkages and was characterized by more rapid rates of hydrolysis at an alkaline pH. These new biodegradable poly(L-aspartic acid-co-PEG)s may have potential applications in the biomedical field. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2949-2959, 1998
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    Highly branched radial block copolymers via dendritic initiation of aliphatic polyesters (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2793-2798 
    Details
    ISSN: 0887-624X
    Keywords: highly branched radial block copolymers ; dendritic initiation ; alipatic polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Living ring opening polymerization of ε-caprolactone initiated from the numerous chain-end hydroxymethyl groups of the analogous dendrimeric and hyperbranched polyesters derived from 2,2-bis(hydroxymethyl) propionic acid is described. By controlling the size of the dendritic macromolecule and the molar ratio of ε-caprolactone, a variety of highly branched radial block copolymers are obtained. Comparison of the results obtained for the dendrimeric and hyperbranched initiators demonstrates that the reactivity of the chain-end hydroxymethyl groups in the dendrimer are significantly greater than in the isomeric hyperbranched case. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2793-2798, 1998
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    Stimuli-responsive polymers. III. Poly(aryl ether ketone amide)s with reversible trans- ↔ cis-4,4′-azobenzene and fixed 2,2′-binaphthyl kinking elements in the main chainDuPont contribution no. 7761. (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2827-2837 
    Details
    ISSN: 0887-624X
    Keywords: stimuli-responsive polymers ; trans-cis isomerization ; NMR spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The low-temperature polycondensation of trans-azobenzene-4,4′-dicarbonyl chloride with (S)-(-)-1,1′-binaphthyl-2,2′-diamine and/or 1,4-bis(3-aminophenoxy-4′-benzoyl)benzene afforded a new series of poly(aryl ether ketone amide)s with both fixed and photoinducible kinking elements positioned randomly along the main chain. In their lower energy, trans-azobenzene configurations, the orange, film-forming materials were amorphous, highly tractable, and thermally stable under air or nitrogen up to about 420°C. Variants endowed with higher loadings of the bent binaphthyl monomer were soluble in a variety of organic solvent media including THF and acetone. The introduction of cis-azobenzene backbone kinks into these materials was carried out by irradiating the polymer solutions with near-UV light. Up to 70% of the azobenzene moieties in these polymers were capable of assuming the higher energy cis-configuration, thus greatly increasing the number of bent or kinked sites positioned along each polymer backbone. In solution, reverse cis → trans isomerization reactions were triggered thermally and were quantitatively tracked by both optical absorbance and 1H NMR spectroscopies. Activation parameters calculated for cis → trans reorganization of the polymer backbone were not dependent upon the chemical composition or molecular weight of the polymers but did exhibit a small dependence upon the nature of the solvent medium used to conduct the isomerization experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2827-2837, 1998
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    Living radical polymerization of methylstyrenes by a stable nitroxyl radical, and stability of the aminoxy chain end (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 269-276 
    Details
    ISSN: 0887-624X
    Keywords: living radical polymerization ; methylstyrene ; MTEMPO ; stability ; aminoxy chain end ; steric hindrance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of 2-, 3-, and 4-methylstyrenes (MeSts) was investigated with benzoyl peroxide (BPO) as an initiator, in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO). The polymerization was performed in bulk for 3.5 h at 95°C, and then continued for a defined time at 125°C, to give the corresponding poly(MeSt)s with narrow polydispersity in high yield. It was found that the polymerization proceeded in accordance with a living mechanism, because the molecular weight of the resulting polymers was proportional to the conversion, and to the reciprocal of the initial concentration of MTEMPO. It was found that steric hindrance between the methyl group of 2-MeSt, and the tetramethyl ones of MTEMPO, significantly contributed to the rate of polymerization, and to the stability of the growing polymer chain end. The stability decreased in the order of 2- 〉 3- 〉 4-MeSt, by occurrence of decomposition, which was caused by disproportionation of the growing chain end. However, the steric hindrance had no effect on the tacticity of the resulting polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36, 269-276, 1998
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    Synthesis and characterization of poly(benzazoles) containing the bicyclo[2.2.2]octane moiety (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 277-281 
    Details
    ISSN: 0887-624X
    Keywords: poly(benzazoles) ; bicyclo[2.2.2]octane ; aromatization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(benzobisoxazoles) (PBOs), poly(benzobisthiazoles) (PBTs) and copolymers thereof containing the 2,5-dihydroxybicyclo[2.2.2]octane moiety have been prepared and studied. The homopolymers were synthesized by the polycondensation of 2,5-dihydroxybicyclo[2.2.2]octane-1,4-dicarboxylic acid with 4,6-diamino-1,3-benzenediol dihydrochloride or 2,5-diamino-1,4-benzenedithiol dihydrochloride in poly(phosphoric acid). Random and block copolymers (PBO-PBT) were also prepared. The polymers were characterized by solubility, X-ray diffraction, spectroscopy (infrared and solid-state 13C nuclear magnetic resonance), and thermal analysis such as differential scanning calorimetry and thermogravimetric analysis. Thermogravimetric analysis showed thermal stability of the polymers above 375°C in air and under argon atmosphere. The polymers exhibited high resistance to organic and inorganic solvents. The polymers were converted to the more stable aromatic polymers via dehydration and retro Diels-Alder reactions of the 2,5-dihydroxybicyclo[2.2.2]octyl moiety by pyrolysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 277-281, 1998
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    Synthesis and thermal analysis of branched and “kinked” poly(ethylene terephthalate) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 309-317 
    Details
    ISSN: 0887-624X
    Keywords: thermal analysis ; branched poly(ethylene terephthalate) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) (PET) was synthesized by self-condensation of bis-(2-hydroxyethyl) terephthalate (BHET). Copolymerization of BHET with ethyl, bis-3,5-(2-hydroxyethoxy) benzoate (EBHEB) and ethyl, 3-(2-hydroxyethoxy) benzoate (E3HEB) yielded copolymers that contain varying amounts of branching and kinks, respectively. Copolymers of BHET with ethyl, 4-(2-hydroxyethoxy) benzoate (E4HEB), in which only the backbone symmetry is broken but without disruption of the linearity, were also prepared for comparison. The composition of the copolymers were established from their 1H-NMR spectra. The intrinsic viscosity of all the copolymers indicated that they were of reasonably high molecular weights. The thermal analysis of the copolymers using DSC showed that both the melting temperatures (Tm) and the percent crystallinity (as seen from the enthalpies of melting) (ΔHm) decreased with increasing comonomer (defect concentration) content, although their glass transition temperatures (Tg) were less affected. This effect was found to be most pronounced in the case of branching, while the effects of kinks and linear disruptions, on both Tm and ΔHm, were found to be similar. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 309-317, 1998
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    Profile of oxidation in irradiated polyethylene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 329-339 
    Details
    ISSN: 0887-624X
    Keywords: ultrahigh molecular weight polyethylene (UHMWPE) ; radiation sterilization ; orthopedic prosthesis ; subsurface oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following gamma irradiation in air which causes bond scission and yields large concentrations of peroxy radicals, maximum oxidation and an increase in crystallinity occurs on the surface of ultrahigh molecular weight polyethylene. Here, bimolecular reactions of peroxy radicals generate carbonyls, mostly ketones. On the polymer surface, peroxy radicals continue to react over time periods of years to generate carbonyls and chain scission. Peroxy radicals in the interior of the polymer abstract hydrogens and form hydroperoxides, inducing chain reactions and a slow but continue increase of ketone. Within the polymer sample, to a decreasing depth with increasing dose, a reduced concentration of oxygen is available to react with radiolytic radicals, so that more efficient crosslinking and a low level of hydroperoxide chain reaction occur. After long periods of time a surface maximum in carbonyl concentration is produced. Heating polyethylene in high pressures of oxygen accelerates the oxidative process. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 329-339, 1998
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    Living cationic polymerization of vinyl ethers with carboxylic acid/tin tetrahalide initiating systems. I. New initiating systems based on acetic acid and selection of Lewis acid and basic additive leading to living polymers with low polydispersity (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3173-3185 
    Details
    ISSN: 0887-624X
    Keywords: cationic polymerization ; living polymerization ; vinyl ether ; initiator ; acetic acid ; tin tetrabromide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic polymerization of isobutyl vinyl ether (IBVE) with acetic acid (CH3COOH)/tin tetrahalide (SnX4: X = Cl, Br, I) initiating systems in toluene solvent at 0°C was investigated, and the reaction conditions for living polymerization of IBVE with the new initiating systems were established. Among these tin tetrahalides, SnBr4 was found to be the most suitable Lewis acid to obtain living poly(IBVE) with a narrow molecular weight distribution (MWD). The polymerization with the CH3COOH/SnBr4 system, however, was accompanied with the formation of a small amount of another polymer fraction of very broad MWD, probably due to the occurrence of an uncontrolled initiation by SnBr4 coupled with protonic impurity. Addition of 1,4-dioxane (1-1.25 vol %) or 2,6-di-tert-butylpyridine (0.1-0.6mM) to the polymerization mixture completely eliminated the uncontrolled polymer to give only the living polymer with very narrow MWD (Mw/Mn ≤ 1.1; Mw, weight-average molecular weight; Mn, number-average molecular weight). The Mn of the polymers increased in direct proportion to monomer conversion, continued to increase upon sequential addition of a fresh monomer feed, and was in good agreement with the calculated values assuming that one CH3COOH molecule formed one polymer chain. Along with these results, kinetic study and direct 1H-NMR observation of the living polymerization indicated that CH3COOH and SnBr4 act as so-called “initiator” and “activator”, respectively, and the living polymerization proceeds via an activation of the acetate dormant species. The basic additives such as 1,4-dioxane and 2,6-di-tert-butylpyridine would serve mainly as a “suppressor” of the uncontrolled initiation by SnBr4. The polymers produced after quenching the living polymerization with methanol possessed the acetate dormant terminal and they induced living polymerization of IBVE in conjunction with SnBr4 in the presence of 1,4-dioxane. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3173-3185, 1998
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    Syntheses of poly(siloxane)-supported zirconocene catalysts and application to olefin polymerizations (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 421-428 
    Details
    ISSN: 0887-624X
    Keywords: poly(siloxane)-supported zirconocene catalysts ; polymerizations of ethene and propene ; copolymerization of ethene with 1-octene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(siloxane)s with bisindenyl, bisfluorenyl, bis(1,2,3,4-tetramethylcyclopentadienyl), bis(2,4,7-trimethylindenyl) and monoindenylmethyl side groups were synthesized by condensation of the corresponding dichlorosilanes and water. For reference, diphenylsilanediol or hydroquinone was also employed in place of water. A series of poly(siloxane)-supported zirconocene catalysts were then prepared from these precursors and applied to ethene and propene polymerizations as well as to the copolymerization of ethene with 1-octene in the presence of methylalumoxane. The polymerization activity of the new supported metallocenes depends drastically upon the substituents in the siloxane backbone. The zirconocene catalysts supported on poly(bisindenylsiloxane) and poly(bisfluorenylsiloxane) give the highest activities for ethene and propene polymerizations, respectively. The weight-average molecular weights of the polymers are also markedly dependent upon the substituents. On the other hand, the molecular mass distributions (MMD) are generally not so sharp, suggesting that the active species formed in these supported catalysts are not uniform. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 421-428, 1998
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    Cyclic(arylene ether) oligomers containing the phenylphosphine oxide moiety (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 519-526 
    Details
    ISSN: 0887-624X
    Keywords: cyclic oligomer ; ring-opening polymerization ; phenylphosphine oxide ; phosphorous ; MALDI-TOF-MS ; poly(arylene ether) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of cyclic(arylene ether) oligomers containing the phenylphosphine oxide moiety has been synthesized by reaction of bis(4-fluorophenyl)phenylphosphineoxide with dihydroxy compounds 1a-d as well as 1,2-dihydro-4-(4-hydroxyphenyl) (2H)phthalazin-1-one in DMF in the presence of anhydrous K2CO3 under high dilution conditions. These cyclic oligomers are amorphous and have high solubility in organic solvents. The MALDI-TOF-MS technique has been used as a powerful tool to analyze these cyclic systems. The cyclic(arylene ether) oligomers readily undergo anionic ring-opening polymerization in the melt at 350°C by using potassium 4,4′-biphenoxide as the initiator, affording linear, high molecular weight poly(arylene ether)s containing the phenylphosphine oxide moiety. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 519-526, 1998
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    Mechanism of the immobilization of surfactants on polymeric surfaces by means of an argon plasma treatment: Influence of the chemical structure of surfactant and substrate (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1829-1846 
    Details
    ISSN: 0887-624X
    Keywords: surface modification ; argon plasma treatment ; poly(ethylene) ; poly(propylene) ; poly(cis-butadiene) ; carboxylic acid groups ; XPS ; SSIMS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article, a study on the mechanism of the immobilization of surfactants on polymeric surfaces by means of an argon plasma treatment is described. The unsaturated surfactant sodium 10-undecenoate [C11(:)] and the saturated surfactant sodium dodecanoate (C12) were immobilized on poly(ethylene) (PE), poly(propylene) (PP), and poly(cis-butadiene) (PB) surfaces. This was accomplished by treating polymeric substrates that were coated with C11(:) or C12 with an argon plasma. Derivatization X-ray Photoelectron Spectroscopy (XPS) and Static Secondary Ion Mass Spectrometry (SSIMS) showed that during the plasma treatment surfactants were covalently coupled to the polymeric surfaces. The chemical structure of both the surfactant and the polymeric substrate influenced the immobilization efficiency. At an optimal treatment time of 5 s, about 28 and 6% of the initial amount of carboxylate groups in the precoated C11(:) and C12 layer, respectively, was retained at the PE surface. The immobilization efficiencies of C11(:) and C12 on PP were about 20 and 9%, respectively. The immobilization efficiency of C11(:) and C12 on PB were both about 7%. The results obtained in this study indicate that the immobilization proceeds via a radical mechanism. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1829-1846, 1998
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    Chemical reactions occurring in the thermal treatment of PC/PMMA blends (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1873-1884 
    Details
    ISSN: 0887-624X
    Keywords: polycarbonate ; poly(methyl methacrylate) ; blends ; exchange reactions ; mass spectrometry ; thermal degradation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical reactions occurring in the thermal treatment of bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) blends have been investigated by nuclear magnetic resonance (NMR), mass spectrometry (MS), size exclusion chromatography (SEC), and thermogravimetry (TG). Our results suggest that in the melt-mixing of PC/PMMA blends, at 230°C, no exchange reactions occur and that only the depolymerization reaction of PMMA has been observed. In the presence of an ester-exchange catalyst (SnOBu2), an exchange reaction was found to occur at 230°C, but no trace of PC/PMMA graft copolymer has been observed. Instead, an exchange reaction between the monomer methyl methacrylate (MMA), generated in the unzipping of PMMA chains, and the carbonate groups of PC has been suggested. This is due to the diffusion of MMA at the interface or even into the PC domains, where it can react with PC producing low molar mass PC oligomers bearing methacrylate and methyl carbonate chain ends and leaving the undecomposed PMMA chains unaffected. The TG curves of PC/PMMA blends prepared by mechanical mixing and by casting from THF show two separated degradation steps corresponding to that of homopolymers. This behavior is different from that of a transparent film of PC/PMMA blend, obtained by solvent casting from DCB/CHCl3, which shows a single degradation step indicating that the degradation rate of PC is increased by the presence of PMMA in the blend. The thermal degradation products obtained by DPMS of this blend consist of methyl methacrylate (MMA), cyclic carbonates arising from the degradation of PMMA and PC, respectively, and a series of open chain bisphenol-A carbonate oligomers with methacrylate and methyl carbonate terminal groups. The presence of the latter compounds suggests a thermally activated exchange reaction occurring above 300°C between MMA and PC. The presence of bisphenol-A carbonate oligomers bearing methyl ether end groups, generated by a thermally activated decarboxylation of the methyl carbonate end groups of PC, has also been observed among the pyrolysis products. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1873-1884, 1998
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    Phthalonitrile cure reaction with aromatic diamines (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1885-1890 
    Details
    ISSN: 0887-624X
    Keywords: phthalonitrile monomer ; thermoset ; curing agent ; processability ; thermal stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phthalonitrile monomers can be polymerized thermally in the presence of small amounts of curing agents into thermosetting polymers. The thermosets exhibit outstanding thermo-oxidative stability, display good mechanical properties, and offer promise as matrices for composite applications. The phthalonitrile cure reaction is typically accomplished with an aromatic diamine, 1,3-bis(3-aminophenoxy)benzene (m-APB), added in the range of 1.5-2% by weight of the monomer in the melt phase. This article addresses the cure reaction with a sulfone-containing diamine, bis[4-(4-aminophenoxy)phenyl] sulfone (p-BAPS), which shows lower volatility as determined from thermogravimetric studies (TGA) compared to m-APB at the processing temperatures typically employed for phthalonitrile cures. Rheometric studies conducted to monitor the viscosity increase during a cure reaction suggest that the cure reaction with m-APB is faster compared to the reaction with p-BAPS. Even though differences are seen in the initial cure rates, the final cured products are similar in terms of the glass transition temperatures and thermal and oxidative stabilities. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1885-1890, 1998
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    Synthesis and properties of soluble aromatic polyimides from 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride and aromatic diamines (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1937-1943 
    Details
    ISSN: 0887-624X
    Keywords: 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride ; aromatic polyimides ; solubility ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic tetracarboxylic dianhydride having crank and twisted noncoplanar structure, 2,2′-bis(3,4-dicarboxyphenoxy)-1,1′-binaphthyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with 2,2′-dihydroxy-1,1′-binaphthyl, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). Binaphthyl-2,2′-diyl-containing novel aromatic polyimides having inherent viscosities up to 0.67 dL/g were obtained by the one-step polymerization process starting from the bis(ether anhydride) and various aromatic diamines. All the polyimides showed typical amorphous diffraction patterns. Most of the polyimides were readily soluble in common organic solvents such as N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and pyridine. These aromatic polyimides had glass transition temperatures in the range of 280-350°C, depending on the nature of the diamine moiety. All polymers were stable up to 400°C, with 10% weight loss being recorded above 485°C in air. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1937-1943, 1998
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    Preparation of an α-cyclodextrin-linked chitosan derivative via reductive amination strategy (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1965-1968 
    Details
    ISSN: 0887-624X
    Keywords: chitosan ; α-cyclodextrin ; reductive amination ; host-guest complex ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 139
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    Photopolymerization of methyl methacrylate using a morpholine-sulfur dioxide charge-transfer complex as the photoinitiator (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1973-1979 
    Details
    ISSN: 0887-624X
    Keywords: photopolymerization ; morpholine-sulfur dioxide complex ; kinetic nonideality ; methyl methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photopolymerization of the vinyl monomer (M) of methyl methacrylate (MMA) was kinetically studied by using near-UV/visible light at 40°C and employing a morpholine (MOR)-sulfur dioxide (SO2) charge-transfer (C-T) complex as the photoinitiator. The rate of polymerization (RP) was found to be dependent on the morpholine: sulfur dioxide mole ratio; the 1 : 2 (MOR-SO2) complex acted as the latent initiator complex C which underwent further complexation with the monomer molecules to give the actual initiating complex I. Using the 1 : 2 (MOR-SO2) C-T complex as the latent initiator, the observed kinetics may be expressed as RP [MOR-SO2]0.27[M]1.10. Benzoquinone behaved as a strong inhibitor. Polymers obtained tested positive for the incorporation of a sulphonate-type end group. Polymerization followed a radical mechanism. Kinetic nonideality as revealed by a low initiator exponent and monomer exponent of greater than unity was explained on the basis of a prominent primary radical termination effect. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1973-1979, 1998
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    A versatile and efficient synthesis of alkoxyamine LFR initiators via manganese based asymmetric epoxidation catalysts (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2161-2167 
    Details
    ISSN: 0887-624X
    Keywords: alkoxyamine ; living free radical polymerizations ; asymmetric epoxidation ; Jacobsen's catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 141
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    Synthesis and characterization of new polyamides derived from 1,6-bis[4-(4-aminophenoxy)phenyl]diamantane (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2185-2192 
    Details
    ISSN: 0887-624X
    Keywords: high-temperature polyamide ; diamantane ; characterization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new polyamides 3 were synthesized by direct polycondensation of the 1,6-bis[4-(4-aminophenoxy)phenyl]diamantane (1) with various dicarboxylic acids. The polyamides had inherent viscosities of 0.45-1.90 dL/g and number-average molecular weights (Mn) of 24,000-110,000. Dynamic mechanical analysis (DMA) reveals that polymers 3 have two relaxations on the temperature scale between -100 and 400°C. Their α relaxations occurred at high temperatures, ranging from 338 to 389°C. Moreover, these polymers remained quite stable at high temperatures and maintained good mechanical properties (G′ = ca. 108 Pa) up to temperatures close to the main transition markedly exceeding 350°C. Due to the bulky diamantane elements and the flexible ether segments, the polymers 3 were amorphous and soluble in a number of organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), and N,N-dimethylacetamide (DMAc). The polyamides 3 have tensile strengths of 56.7-90.2 MPa, elongation to breakage values of 7.5-27.7%, and initial moduli of 1.8-2.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2185-2192, 1998
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    Novel mechanism for the formation of long-chain branching in polyethylene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2889-2898 
    Details
    ISSN: 0887-624X
    Keywords: long-chain branching ; polymerization ; catalysts ; polyethylene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyethylene produced by a vanadium-based polymerization catalyst contains long-chain branching as determined by NMR and rheology, even though the polymer has very low levels of vinyl unsaturation. A new mechanism is proposed for the formation of the long-chain branching, which involves C—H bond activation of the polyethylene backbone through a σ-bond metathesis reaction, followed by ethylene insertion at the new V—C bond. Consistent with the proposed C—H bond activation mechanism, the polymerization catalyst was also found to insert ethylene into the C—H bonds of alkanes such as heptane. A bridged metallocene catalyst was also found to activate C—H bonds of alkanes suggesting this new mechanism may explain the formation of long-chain branching in some metallocene-produced polyethylene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2889-2898, 1998
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    Kinetic and ESR studies on radical polymerization of methyl methacrylate in the presence of fullerene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2905-2912 
    Details
    ISSN: 0887-624X
    Keywords: radical polymerization ; fullerene 60 ; methyl methacrylate ; fullerene radical ; ESR spectrum ; starlike copolymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of fullerene (C60) on the radical polymerization of methyl methacrylate (MMA) in benzene was studied kinetically and by means of ESR, where dimethyl 2,2′-azobis(isobutyrate) (MAIB) was used as initiator. The polymerization rate (Rp) and the molecular weight of resulting poly(MMA) decreased with increasing C60 concentration ((0-2.11) × 10-4 mol/L). The molecular weight of polymer tended to increase with time at higher C60 concentrations. Rp at 50°C in the presence of C60 (7.0 × 10-5 mol/L) was expressed by Rp = k[MAIB]0.5[MMA]1.25. The overall activation energy of polymerization at 7.0 × 10-5 mol/L of C60 concentration was calculated to be 23.2 kcal/mol. Persistent fullerene radicals were observed by ESR in the polymerization system. The concentration of fullerene radicals was found to increase linearly with time and then be saturated. The rate of fullerene radical formation increased with MAIB concentration. Thermal polymerization of styrene (St) in the presence of resulting poly(MMA) seemed to yield a starlike copolymer carrying poly(MMA) and poly(St) arms. The results (r1 = 0.53, r2 = 0.56) of copolymerization of MMA and St with MAIB at 60°C in the presence of C60 (7.15 × 10-5 mol/L) were similar to those (r1 = 0.46, r2 = 0.52) in the absence of C60. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2905-2912, 1998
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    Synthesis and chain structure of ethylene terephthalate-ε-caprolactone copolyesters (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2961-2969 
    Details
    ISSN: 0887-624X
    Keywords: segmented TCL copolyesters ; hard segment content ; chemical structure ; sequence structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of ethylene terephthalate-ε-caprolactone copolyesters (TCL) with different hard segment contents were synthesized and characterized by GPC, NMR, and DSC. The analysis from high-field 1H-NMR reveals that the transesterification between ET and CL segments during synthesis is unavoidable, so TCL copolyesters are segmented copolyesters with certain random properties, as shown by the specific chemical and sequence structure of TCL copolyester chains and as confirmed by their crystallization behavior. The stress-strain test shows that TCL copolyesters with different hard segment contents may possess rubberlike or toughening plastic mechanical properties. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2961-2969, 1998
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    Polyketomalonates by catalytic oxidation of glycerol. I (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2993-2994 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    Novel thermoplastic elastomers. I. Synthesis and characterization of star-block copolymers of PSt-b-PIB arms emanating from cyclosiloxane coresPart XVIII of the series New Polyisobutylene Stars. For part XVII, see: J. S. Shim, S. Asthana, N. Omura, and J. P. Kennedy, Polym. Prepr., 39 (1), 196 (1998). (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2997-3012 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of novel thermoplastic elastomers consisting of multiple polystyrene-b-polyisobutylene (PSt-b-PIB) arms emanating from cyclosiloxane cores is described. The synthesis involved the sequential living cationic block copolymerization of styrene (St) and isobutylene (IB), followed by quantitative allylic end-functionalization of the living PSt-b-PIB+ to produce PSt-b-PIB—CH2— CH=CH2 prearms, and finally linking by hydrosilation of these prearms with Si—H-containing cyclosiloxanes (e.g., 2,4,6,8,10,12-hexamethylcyclohexasiloxane, DH6). Two types of star-blocks, namely primary and higher-order star-blocks, were prepared: Primary star-blocks containing 3-9 PSt-b-PIB arms were obtained by using various cyclosiloxanes (DH6 to DH12) and a close to exact stoichiometry between the Si—H and allyl groups, [Si—H]/[C=C] ∼ 1, in the essential absence of moisture ([H2O] ∼ 100 ppm). Higher-order star-blocks consisting of 13-24 PSt-b-PIB arms radiating from complex coupled cyclosiloxanes were prepared by the use of Si—H/allyl ratios significantly larger than unity ([Si—H]/[C=C] = 2-3) in the presence of controlled amounts of moisture ([H2O] ∼ 600 ppm). Reaction conditions (temperature, concentration, stoichiometry, solvent nature, catalyst concentration, etc.) for efficient syntheses have been developed. The products were characterized by 200 and 600 MHz 1H-NMR spectroscopy and triple-detector (RI, UV, LLS) GPC. The microstructure of the condensed cores in the higher-order star-blocks was studied by 2D-NMR (HMQC) spectroscopy, and the number of cyclosiloxane rings in the cores (i.e., the content (wt %) of cores in the star-blocks) was determined. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2997-3012, 1998
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    Synthesis and properties of phosphorus-containing polyesters derived from 2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)-1,4- hydroxyethoxy phenylene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3051-3061 
    Details
    ISSN: 0887-624X
    Keywords: flame retardancy ; polyester ; activation energy of degradation ; LOI ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of phosphorous-containing aliphatic polyesters were synthesized by high-temperature solution condensation of 2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)-1,4-hydroxyethoxy phenylene (III) with various aromatic acid chlorides in o-dichlorobenzene. All polyesters are amorphous and readily soluble in many organic solvents such as DMAc, NMP, DMSO, and o-dichlorobenzene at room temperature or upon heating. These polyesters are thermally quite stable. The glass transition temperatures of these aliphatic polyesters ranged from 126.6 to 162.2°C. The degradation temperatures (Td onset) in nitrogen ranged from 424 to 448°C, and the char yields at 700°C are 20-32%. The activation energies of degradation ranged from 160.9 to 226.0 kJ/mol. The LOIs of these polyesters ranged from 36 to 43. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3051-3061, 1998
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    Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3089-3095 
    Details
    ISSN: 0887-624X
    Keywords: radiation ; thermal degradation ; poly(vinyl chloride) ; poly(vinyl alcohol) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089-3095, 1998
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    Pulsed-plasma polymerization of 1-vinyl-2-pyrrolidone: Synthesis of a linear polymer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3121-3129 
    Details
    ISSN: 0887-624X
    Keywords: pulsed-plasma ; 1-vinyl-2-pyrrolidone ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The RF plasma induced polymerization of 1-vinyl-2-pyrrolidone was examined under variable duty-cycle pulsed-plasma conditions. Large-scale progressive changes in the composition of the resultant polymeric films were observed with sequential changes in the plasma duty cycle employed during polymerization, all other plasma variables held constant. The film compositional changes obtained are in the direction of increased retention of the lactam ring of the monomer in the resultant polymers as the duty cycles employed (i.e., the ratio of plasma on to plasma off times) were decreased. Particularly significant are the relatively linear polymeric structures obtained under the exceptionally low-average power deposition conditions made accessible with the pulsed plasma technique. XPS and FTIR spectroscopic examination of these latter films reveal compositions that are similar to those obtained by conventional (i.e., nonplasma) synthesis of the linear polymer. The film chemistry controllability demonstrated in the present study is achieved while maintaining the many advantages of the plasma polymerization approach for surface modifications. This work provides additional support for use of the pulsed operational mode as an effective means of film chemistry control, in particular extending the plasma polymerization technique to include synthesis of linear polymers, in lieu of the more highly crosslinked structures typically produced in conventional continuous-wave plasma polymerization processes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3121-3129, 1998
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    Synthesis, geometric structure, and properties of poly(phenylacetylenes) with bulky para-substituents (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3157-3163 
    Details
    ISSN: 0887-624X
    Keywords: poly(phenylacetylene) ; transition metal catalyst ; metathesis polymerization ; geometric structure ; gas permeability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phenylacetylenes (PAs) with bulky substituents (adamantyl, tert-butyl, and n-butyl groups) at the para-position polymerized in good yields with Fe, Rh, Mo, and W catalysts. The formed polymers were soluble, and their number-average molecular weights were in the range of thousands to hundred thousands. Whereas it is known that the poly(PA) obtained with the Fe catalyst is an insoluble cis-cisoidal polymer, the present polymers formed with the same catalyst were totally soluble in many solvents such as benzene and CHCl3. The 1H- and 13C-NMR and DSC data revealed that both of the polymers formed with the Fe and Rh catalysts had virtually all-cis structures, while those with the Mo and W catalysts had cis-rich and trans-rich structures, respectively. Cis-cisoidal and cis-transoidal structures of para-substituted poly(PAs) could not be distinguished because of their good solubility. The bulky substituents raised the temperature of cis-trans isomerization and improved the thermal stability of the polymers. Poly(p-t-BuPA) showed gas permeability higher than that of poly(PA). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3157-3163, 1998
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    A positive-working photosensitive alkaline-developable polyimide with a highly dimensional stability and low dielectric constant based on poly(amic acid) as a polyimide precursor and diazonaphthoquinone as a photosensitive compound (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3197-3197 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Tributylstannylated silicic acid as precursor of organofunctionalized silica gel (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 655-663 
    Details
    ISSN: 0887-624X
    Keywords: water glass ; bis(tributyltin)oxide ; tributylstannylated silicic acid ; functionalized silica gel ; silane coupling agent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tributylstannylated silicic acid (TBSA), which was regarded as a protected polymeric silanol against self-condensation to give silica gel, was newly prepared from the reaction of water glass (WG) and bis(tributyltin) oxide (TBO). The ratios of Si/Sn contained in TBSA were determined by gravimetric analysis to be in the range of 2-3. The gelation of TBSA in usual organic solvents such as hexane, benzene, and dichloromethane was not observed over 3 weeks. In addition, TBSA was shown to be a convenient precursor for the preparations of silica gel modified with organofunctional groups. From the reaction of TBSA with trimethoxysilanes and aromatic alcohols, the silica gels havingorganofunctional groups were obtained with the elimination of a tributyltin group. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 655-663, 1998
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    Convenient approach to novel functional substituted and branched poly(silylenemethylenes) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 725-735 
    Details
    ISSN: 0887-624X
    Keywords: organosilicon polymer ; poly(silylenemethylene) ; silyl triflate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel poly(silylenemethylenes) have been prepared by the ring-opening polymerization of 1,3-disilacyclobutanes followed by a protodesilylation reaction with triflic acid. The silicon-aryl bond cleavage could be controlled by using different leaving groups, for instance phenyl- and para-anisyl substituents. The reactions of the triflate derivatives with organomagnesium compounds, LiAlH4, amines, or alcohols gave functional substituted poly(silylenemethylenes). Hydrosilylation reactions or reductive coupling with potassium-graphite led to organosilicon network-polymers, which may serve as suitable precursors for silicon carbide and Si/C/N-based materials. The structures of the polymers were identified by NMR spectroscopy (29Si, 13C, 1H). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 725-735, 1998
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    Synthesis, homopolymerization, and block copolymerization of N-ethyl-2-ethynyl-pyridinium trifluoromethanesulfonate with styrene and butadiene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 703-712 
    Details
    ISSN: 0887-624X
    Keywords: synthesis ; homopolymerization ; block copolymerization ; N-ethyl-2-ethyl-pyridinium ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel acetylenic monomer 2-N-ethyl pyridinium trifluoromethane sulfonate (2EPyEtTf) was synthesized and polymerized. Diblock copolymers of 2EPyEtTf with styrene and with butadiene were prepared. Initiation of the polymerization by living anionic polystyryl--Li+ and polybutadienyl--Li+ (Scheme 1) resulted in polystyrene-block-poly(N-ethyl-2-ethynylpyridinium trifluoromethanesulfonate) (PS57PA8), and polybutadiene -block-poly(N-ethyl-2-ethynylpyridinium trifluoromethanesulfonate) (PB30PA8). These amphiphilic block molecules contain rigid, conjugated, and strongly hydrophilic polyacetylene chain fragments attached to hydrophobic polystyrene or flexible polybutadiene chain fragments. The structure of these copolymers was studied by FTIR, UV-visible, and NMR spectroscopy. GPC and viscometry were also used to obtain information on the molecular mass and the molecular mass distribution. Thermal behavior was investigated by means of TGA and DSC. Both block copolymers were shown to form stable monolayers at the air-water interface. The positively charged rigid polyacetylene portion of the copolymer is believed to be partially submerged, while the more flexible hydrophobic chains are forced out of the water. Multilayers of PB30PA8 deposited using the Langmuir-Blodgett technique were found to be less uniform than in the case of the previously reported polystyrene-block-poly(2EPyMeTf) (PS12PA4) copolymer (Balogh et al., Macromolecules, 29, 1996). Polycation-polyanion self-assembly deposition was also investigated, using polystyrenesulfonate (PSS) as polyanion. While PS57PA8/PSS layer-by-layer deposition was not uniform, it was found that PB30PA8/PSS gave homogenous and stable films on hydrophilic glass substrates. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 703-712, 1998
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    New aromatic benzazole polymers II: Synthesis and conductivity of benzobisthiazole-co-polymers incorporated with 4-N,N-dimethylaminotriphenylamine groups (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 713-724 
    Details
    ISSN: 0887-624X
    Keywords: poly(benzobisthiazole) ; copolymers ; 4-N,N-dimethylaminotriphenylamine ; conducting polymers ; iodine doping ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New aromatic benzobisthiazole copolymers containing 10-70 mol % of 4-N,N-dimethylamino-triphenylamine functionality were prepared from the respective dinitrile or dicarboxylic acid monomers, terephthalic acid, and 2,5-diamino-1,4-benzene-dithiol dihydrochloride in polyphosphoric acid. At the first approximation, the copolymers containing 10 mol % or less of the triarylamino moieties in the polymer chains still preserve the capability to form anisotropic (nematic) solutions at 10 wt % polymer concentration. This is an important requirement for processing the copolymers into fibers and films with good to excellent mechanical properties. Films with good mechanical integrity were cast from the dilute methanesulfonic acid solutions of the copolymers under reduced pressure. They showed electrical conductivity values of the order of 10-11-10-10 S/cm in pristine state, with four to seven orders of magnitude increase upon exposure to mild oxidizing agents such as iodine vapor. On the contrary, the parent polymer, poly(p-phenylene benzobisthiazole) is an insulator with conductivity of less than 10-12 S/cm, and its conductivity does not improve at all with exposure to iodine vapor. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 713-724, 1998
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    Synthesis, liquid crystallinity, and mechanical properties of thermotropic polyquinolines (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 749-759 
    Details
    ISSN: 0887-624X
    Keywords: polyquinoline ; liquid crystalline polymer ; thermotropic ; mechanical property ; substituted polyquinoline ; flexible groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermotropic liquid-crystalline polyquinolines with high molecular weights, i.e., poly[2,2′-(α,ω-dioxyphenylene (or -dioxybiphenylene) alkane)-6,6′-(4,4′-dioxybiphenyl)-bis(4-phenylquinoline)]s (P-H-B1Mns or P-H-B2Mns), were synthesized by polycondensation of 4,4′-bis(4-amino-3-benzoylphenoxy)biphenyl and α,ω-bis(4-acetophenoxy (or -acetobiphenoxy))alkanes. For P-H-B1Mn series, the Tm and Ti were in the range of 129-230°C and 156-254°C, respectively, while for the P-H-B2Mn series, those were 182-275°C and 217-309°C, respectively. The introduction of both the dioxybiphenylene group and an alkylene spacer induced thermotropic liquid crystallinity in the polyquinoline, although the introduction of the alkylene spacer alone did not induce it. In addition, polyquinolines substituted with methyl, methoxy, and chloro groups exhibited larger mesophase temperature ranges as well as higher Tms and Tis than the unsubstituted ones. Tensile strengths of these thermotropic polyquinolines were considerably high in the range of 770 to 1170 kgf/cm2. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 749-759, 1998
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    Controlled free radical ring-opening polymerization and chain extension of the “living” polymer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 761-771 
    Details
    ISSN: 0887-624X
    Keywords: ring-opening polymerization ; “living” free radical polymerization ; stable free radical ; 2-methylene-1,3-dioxepane ; 2,2,6,6-tetramethyl-1-piperidinyloxy free radical ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free radical ring-opening polymerization of 2-methylene-1,3-dioxepane (MDP) in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) has been achieved to afford a chain polyester (PMDP) with di-t-butyl peroxide (DTBP) as an initiator at 125°C. The polydispersity of the polymers decreases as the concentration of TEMPO is increased. At high TEMPO concentrations, the polydispersity as low as 1.2 was obtained, which is below the theoretical lower limit for a conventional free radical polymerization. A linear relationship between the number-average molecular weight (Mn) and the monomer conversion was observed with the best-fit line passing very close to the origin of the Mn-conversion plot. The isolated and purified TEMPO-capped PMDP polymers have been employed to prepare chain extended polymers upon addition of more MDP monomer. These results are suggestive of the “living” polymerization process. A possible polymerization mechanism might involve thermal homolysis of the TEMPO-PMDP bonds followed by the addition of the monomers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 761-771, 1998
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    Curing reaction of biphenyl epoxy resin with different phenolic functional hardeners (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 773-783 
    Details
    ISSN: 0887-624X
    Keywords: biphenyl epoxy ; hardener ; cure kinetics ; cure mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The investigation of cure kinetics and relationships between glass transition temperature and conversion of biphenyl epoxy resin (4,4′-diglycidyloxy-3,3′,5,5′-tetramethyl biphenyl) with different phenolic hardeners was performed by differential scanning calorimeter using an isothermal approach over the temperature range 120-150°C. All kinetic parameters of the curing reaction including the reaction order, activation energy, and rate constant were calculated and reported. The results indicate that the curing reaction of formulations using xylok and dicyclopentadiene type phenolic resins (DCPDP) as hardeners proceeds through a first-order kinetic mechanism, whereas the curing reaction of formulations using phenol novolac as a hardener goes through an autocatalytic kinetic mechanism. The differences of curing reaction with the change of hardener in biphenyl epoxy resin systems were explained with the relationships between Tg and reaction conversion using the DiBenedetto equation. A detailed cure mechanism in biphenyl-type epoxy resin with the different hardeners has been suggested. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 773-783, 1998
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    Synthesis and properties of poly(oxyethylene)s containing thioether, sulfoxide, or sulfone groups (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 793-801 
    Details
    ISSN: 0887-624X
    Keywords: poly(oxyethylene) ; thioether ; sulfoxide ; sulfone ; copolymer ; solubility ; glass transition temperature ; substitution ; oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly[oxy(ethylthiomethyl)ethylene] (ETE) was prepared from poly[oxy (chloromethyl)ethylene] (CE) by reaction with sodium ethanethiolate. Sulfoxide and sulfone analogues were synthesized by oxidation of the poly[oxy(ethylthiomethyl)ethylene]. By changing the chloromethyl/sodium ethanethiolate ratio, poly[oxy (chloromethyl)ethylene-co-oxy(ethylthiomethyl)ethylene] (CE-ETEs) were easily made. Poly[oxy(ethylsulfinylmethyl)ethylene] (ESXE), poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXEs), poly[oxy(ethylsulfonylmethyl)ethylene] (ESE), and poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene] (CE-ESEs) were obtained by oxidation of ETE or CE-ETEs. There was little if any chain degradation. The (co)polymer structures were confirmed by FTIR and 1H-NMR spectroscopic studies. Their thermal properties were studied by DSC and TGA. Tgs of ETE, ESXE, and ESE were -57, 36, and 57°C, respectively, and Td,os (initial decomposition temperature, TGA) were 331, 198, and 308°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 793-801, 1998
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    Graft copolymers prepared by ethoxylation of polyamide 12 and poly(ethylene-co-vinyl alcohol) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 803-811 
    Details
    ISSN: 0887-624X
    Keywords: grafting ; poly(amide-graft-ethylene oxide) ; poly(ethylene-co-vinyl alcohol-graft-ethylene oxide) ; ethoxylation ; anionic polymerization of ethylene oxide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymers consisting of polyamide 12 or poly(ethylene-co-vinyl alcohol) as backbone polymers and side chains of poly(ethylene oxide) have been synthesized. The amide and hydroxyl groups of the backbone polymers were used as initiation sites for the polymerization of ethylene oxide (EO). Potassium tert-butoxide was used for ionization of the active groups, and the polymerization of EO was carried out in dimethyl sulfoxide. The graft copolymers were characterized with respect to molecular weight and composition using elemental analysis, 1H-NMR, gel permeation chromatography, and FTIR. The size of the side chains varied between 300 and 1000 g/mol. Thermal properties were examined by DSC. The graft copolymers showed increasing crystallinity and increasing melt temperature with increasing molecular weight of the side chains. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 803-811, 1998
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    Synthesis and characterization of new polyamides containing adamantyl and diamantyl moieties in the main chain (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 785-792 
    Details
    ISSN: 0887-624X
    Keywords: polyamides ; adamantane ; diamantane ; synthesis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work synthesized a series of new polyamides by direct polycondensation of 1,3-bis[4-(4-carboxyphenoxy)phenyl]adamantane (I) with various diamines. The diacid I was synthesized from 1,3-bis(4-hydroxyphenyl)adamantane in two steps. Polyamides III were soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and pyridine. The polyamides had medium inherent viscosities of 0.30-0.55 dL/g and number-average molecular weights (Mn) of 22,000-36,000. The polyamides IIIa and IIIb had tensile strengths of 59.8 and 77.5 MPa, elongation to breakage values of 5.8 and 7.6%, and initial moduli of 1.9 and 1.8 GPa, respectively. Their glass transition temperatures were found to be 219-295°C by means of differential scanning calorimetry (DSC). Dynamic mechanical analysis (DMA) reveals that the incorporation of rigid and bulky diamantane into polyamides IIIa and IIIb leads to high glass transition temperatures (Tgs), at 299 and 286°C, respectively. The decomposition temperatures of polyamides III at a 5% weight loss ranged from 388 to 416°C in air and from 408 to 435°C in N2 atmosphere. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 785-792, 1998
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    Case studies and literature review on the estimation of copolymerization reactivity ratios (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 813-822 
    Details
    ISSN: 0887-624X
    Keywords: copolymerization reactivity ratios ; RREVM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enhanced features of a computer program (RREVM) for the estimation of copolymerization reactivity ratios using statistically sound techniques are illustrated with experimental and simulated case studies. In parallel, a literature review is given on the estimation of reactivity ratios. Both aspects are extensions based on the articles by Dube et al.1 and Rossignoli and Duever.2 © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 813-822, 1998
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    Synthesis and properties of poly(amide-imide)s based on the diimide-diacid condensed from 2,2′- bis(4-aminophenoxy)biphenyl and trimellitic anhydride (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1169-1177 
    Details
    ISSN: 0887-624X
    Keywords: poly(amide-imide)s ; 2,2′-bis(4-trimellitimidophenoxy) biphenyl ; solubility ; 2,2′-bis(4-aminophenoxy)biphenyl ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new dicarboxylic acid having a kinked structure was synthesized from the condensation of 2,2′-bis(4-aminophenoxy)biphenyl and trimellitic anhydride. A series of biphenyl-2,2′-diyl-containing aromatic poly(amide-imide)s having inherent viscosities of 0.23-0.94 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid II with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in a variety of organic solvents including NMP and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films of these polymers could be cast from DMAc or NMP solutions. The glass transition temperatures of these polymers were in the range of 227-261°C and the 10% weight loss temperatures were above 520°C in nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1169-1177, 1998
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    Hydrogels by atom transfer radical polymerization. I. Poly(N-vinylpyrrolidinone-g-styrene) via the macromonomer method (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 823-830 
    Details
    ISSN: 0887-624X
    Keywords: atom transfer radical polymerization ; poly(N-vinylpyrrolidinone-g-styrene) ; macromonomer method ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atom transfer radical polymerization has been used to prepare well-defined vinyl macromonomers of polystyrene using vinyl chloroacetate as an initiator. Because styrene and vinyl chloroacetate do not copolymerize, no branching or incorporation of the initiator into the backbone was observed. Macromonomers of several molecular weights were prepared and copolymerized free radically with N-vinylpyrrolidinone in varying feed ratios in order to produce poly(NVP-g-Sty) graft copolymers. The macromonomers used were of sufficiently high molecular weight to form physical crosslinks in solvents which favor the hydrophilic NVP, such as water, which prevent the copolymer from dissolving and cause it to swell. These materials, therefore, formed hydrogels of swellabilities in water exceeding 95%, depending on the amount of styrene that was incorporated into the copolymer. Limitations of and alternatives to this method are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 823-830, 1998
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    Cationic copolymerization of cyclic ketene acetals: The effect of substituents on reactivity (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 861-871 
    Details
    ISSN: 0887-624X
    Keywords: 2-methylene-1,3-dioxane ; 4-methyl-2-methylene-1,3-dioxane ; 4,4,6-trimethyl-2-methylene-1,3-dioxane ; 2-methylene-1,3-dioxolane ; 4-methyl-2-methylene-1,3-dioxolane ; 4,5-dimethyl-2-methylene-1,3-dioxolane ; cationic copolymerization ; reactivity ratio ; relative reactivity ; ring-retained polymerization ; cyclic ketene acetals ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic copolymerizations of 4-methyl-2-methylene-1,3-dioxane, 2 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4,4,6-trimethyl-2-methylene-1,3-dioxane, 3 (M1), with 2-methylene-1,3-dioxane, 1 (M2); of 4-methyl-2-methylene-1,3-dioxolane, 5 (M1), with 2-methylene-1,3-dioxolane, 4 (M2); and of 4,5-dimethyl-2-methylene-1,3-dioxolane, 6 (M1), with 2-methylene-1,3-dioxolane, 4 (M2) were conducted. The reactivity ratios for these four types of copolymerizations were r1 = 1.73 and r2 = 0.846; r1 = 2.26 and r2 = 0.310; r1 = 1.28 and r2 = 0.825; r1 = 2.23 and r2 = 0.515, respectively. The relative reactivities of these monomers towards cationic polymerization are: 3 〉 2 〉 1; and 6 〉 5 〉 4. With both five- and six-membered ring cyclic ketene acetals, the reactivity increased with increasing methyl substitution on the ring. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 861-871, 1998
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    Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1329-1340 
    Details
    ISSN: 0887-624X
    Keywords: poly(amide acid) ammonium salts ; poly(amide acid)s ; water-soluble polyimide precursors ; UV-vis absorption spectra ; charge transfer ; solubility ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet-visible (UV-vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H2O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329-1340, 1998
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    Polyurethanes crosslinked by metals and their complexes with crown ether (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1379-1386 
    Details
    ISSN: 0887-624X
    Keywords: polyrethanes ; crown ether ; metal complexes ; X-ray scattering ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two types of crosslinked polyurethanes (PU) have been synthesized: (a) PU crosslinked by metal ions (Cu2+ and Co2+), and (b) PU crosslinked by the complexes of metals with crown ether. Using X-ray scattering under small and wide angles the peculiarities of the structure of networks have been investigated. It was found that PU crosslinked by the metal crown ether complexes have a looser structure because of the bulky crosslink and diminished molecular mobility of the chains between two crosslinks, as was proven by the dielectric spectroscopy method. The X-ray and IR data have allowed proposing a scheme of the structure of the crosslinked PU with various types of crosslinks. The structures discovered may be considered as similar to metal catenandes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1379-1386, 1998
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    New polymer syntheses. XCVI. Star-shaped LC-polyesters derived from β-(4-hydroxyphenyl)propionic acid and 4-hydroxybenzoic acid (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1387-1395 
    Details
    ISSN: 0887-624X
    Keywords: star-shaped polyesters ; nematic phase ; phloritic acid ; spirobis indane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Star-shaped polyesters were prepared by polycondensation of tetraacetoxyspirobis(indane) and a 1 : 1 mixture of silylated β-(4-acetoxyphenyl)propionic acid and silylated 4-acetoxybenzoic acid. The lengths of the star arms were systematically varied, and the influence of the star center on the stability of the nematic phase was studied. It was found that on the average more than 10 monomer units per star arm are required to stabilize a homogeneous LC-phase. Furthermore, a second class of star-shaped polyesters consisting of β-(4-hydroxyphenyl)propionic acid (HPPA), 4-hydroxybenzoic acid (HBA), and 6-hydroxy-2-naphthoic acid (HNA) was prepared. This ternary copolyester proved to reduce the crystallinity but to stabilize the LC-character. A homogeneous nematic melt was obtained with 6 monomer units per star arm. This interpretation is based on optical microscopy which provides a static picture of the biphasic situation. Therefore, a preliminary study of the melt rheology was included, which proved that the typical LC-character of the melt was detectable ateven shorter star arms due to the shear orientation. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1387-1395, 1998
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    Structural effect of polymeric acid dopants on the characteristics of doped polyaniline composites: Effect of hydrogen bonding (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1431-1439 
    Details
    ISSN: 0887-624X
    Keywords: polyaniline ; polymeric acid dopant ; conducting polymer ; doping level ; chain alignment ; conductivity ; hydrogen bonding ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conductivities of polyaniline (PANi) composites doped with the copolymeric acids such as poly(methyl methacrylate-co-p-styrenesulfonic acid) (PMMA-co-SSA), poly(styrene-co-p-styrenesulfonic acid) (PS-co-SSA), and poly(methyl methacrylate-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (PMMA-co-AMPS) were investigated as a function of the acid content in the copolymeric acid dopants. With the fixed ratio of acid to aniline (1/1) in the PANi composites, the conductivities of the copolymeric acid-doped PANis decreased as the acid content in the copolymeric acids decreased. This could be attributed to the nonacidic units in the copolymeric acids which seemed to prevent adjacent acid groups from doping the PANi. Among the three kinds of copolymeric acid dopants, the PMMA-co-SSA series doped the PANi most effectively, and consequently, the PMMA-co-SSA-doped PANi composites showed the highest conductivities. The lack of conductivities of the PMMA-co-AMPS-doped PANi composites seems to be due to the doping ability of the AMPS groups. The higher conductivities of the PMMA-co-SSA-doped PANi composites rather than the PS-co-SSA-doped ones were attributed to the hydrogen bonding formed between the carbonyl groups in MMA and the amine groups in aniline which may hinder the phase separation and induce more homogeneous mixing and efficient doping. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1431-1439, 1998
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    Synthesis and spinning of a thermotropic liquid crystal copolyester containing a semirigid cycloaliphatic spacer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1473-1480 
    Details
    ISSN: 0887-624X
    Keywords: thermotropic polymers ; liquid crystalline polymers ; semirigid spacers ; melt spinning ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A thermotropic, liquid crystalline copolyester, based on 2-chlorohydroquinone, 1,4-cyclohexanedimethanol and terephthaloyl chloride, has been synthesized and melt spun. The cyclohexanedimethylene moiety acts as a semirigid spacer, introducing flexibility while preserving the thermotropic nature of the polymer. Melt-spun fibers were observed to have a high degree of molecular alignment owing to the nematic nature of the melt. Both polymer and fiber properties have been characterized. Characterization techniques used to this end include elemental analysis, hot-stage polarized light microscopy, scanning electron microscopy, dilute solution viscometry, Fourier transform infrared spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1473-1480, 1998
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    Synthesis and properties of copolymers from 2-hydroxyethyl methacrylate-linked nonsteroidal antiinflammatory agents with methacrylic acid (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1481-1490 
    Details
    ISSN: 0887-624X
    Keywords: ibuprofen ; ketoprofen ; naproxen ; copolymer reactivity ; thermal stability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three nonsteroidal antiinflammatory drugs, 2-(4-isobutylphenyl)-propionic acid (ibuprofen), 2-(3-benzoylphenyl)-propionic acid (ketoprofen), and 2-(6-methoxy-2-naphthyl)-propionic acid (naproxen), were covalently linked with 2-hydroxyethyl methacrylate (HEMA). The drug-linked HEMA (M1) (ibuprofen-linked HEMA abbreviated as HI; ketoprofen-linked HEMA as HK, and naproxen-linked HEMA as HN), were respectively copolymerized with methacrylic acid (M2), MA, to obtain macromolecular prodrugs. The compositions of the copolymers were determined by means of a 1H-NMR spectroscopy and monomer reactivity ratios were estimated using the Kelen-Tüdös linear differential equation. The reactivity ratios are: r1 = 0.101 ± 0.012, r2 = 1.071 ± 0.065 for HI-MA; r1 = 0.344 ± 0.066, r2 = 0.966 ± 0.032 for HN-MA, and r1 = 0.650 ± 0.182, r2 = 1.032 ± 0.106 for HK-MA, respectively. The monomer reactivity toward to MA radical estimated from 1/r2 values is almost same for all three monomers (1/r2 ∼ 1). The glass transition temperatures of three drug-linked homopolymers go hand in hand with the steric hindrance of three drugs, i.e., ketoprofen 〉 naproxen ≫ ibuprofen calculated the minimum energy by computer molecular modeling. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1481-1490, 1998
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    Synthesis and radical polymerization of a vinyl monomer having a sulfonylacylurea moiety and hydrolysis of the obtained polymer (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1515-1519 
    Details
    ISSN: 0887-624X
    Keywords: sulfonyl isocyanate ; acrylamide ; sulfonylurea ; radical polymerization ; hydrolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical polymerization of N-acryloyl-N′-(p-tolylsulfonyl)urea (2), prepared easily by the reaction of p-toluenesulfonyl isocyanate with acrylamide, was carried out in DMF, DMSO, or NMP at 60°C by use of AIBN as an initiator to give a polymer 3 in a good yield. Copolymerization parameters of 2 were evaluated by the copolymerization with MMA. Polymer 3 was readily hydrolyzed in an aqueous NaOH solution (1M) at room temperature to give poly(acrylic acid). The reason for the higher activity for hydrolysis of 3 compared to an ordinary amide is discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1515-1519, 1998
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    Sequence distributions versus catalyst site behavior of in situ blends of polypropylene and poly(ethylene-co-propylene) (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1527-1542 
    Details
    ISSN: 0887-624X
    Keywords: high-impact polypropylenes ; 13C-NMR ; Markovian statistics ; reactivity ratio product ; catalyst site distribution ; sequence distributions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential polymerizations of first propylene and then ethylene, propylene mixtures with the same Ziegler-Natta catalyst system produce in situ blends known as high-impact polypropylenes. Over 100 high-impact polypropylenes are characterized in terms of weight fractions and sequence distributions for isotactic polypropylene, atactic polypropylene, an amorphous ethylene propylene copolymer, and a crystalline ethylene propylene copolymer. The apparent r1r2 behaviors of the E/P copolymers suggest that the amorphous and crystalline E/P copolymers principally arise from different types of catalyst sites as opposed to originating strictly from compositional heterogeneities. The amorphous copolymers consistently have r1r2 values close to unity over a broad range of compositions, while the corresponding crystalline copolymers have apparent r1r2 values that range from 2 to over 20. An apparent r1r2 close to unity not only reflects random sequencing but also indicates a narrow compositional distribution. This r1r2 result indicates that the amorphous E/P copolymers are produced from a singular type of catalyst site. The higher r1r2 values shown by the crystalline E/P copolymers indicate broad compositional distributions that are produced by a different type or types of catalyst sites. The ratio of amorphous to crystalline ethylene, propylene copolymers is nominally around 80/20 over a broad range of impact copolymer compositions. The consistency of this result suggests that the two basic types of catalyst sites producing E/P copolymers are also in an approximate 80/20 ratio. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1527-1542, 1998
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    Optical emission diagnostics in cascade arc plasma polymerization and surface modification processes (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1583-1592 
    Details
    ISSN: 0887-624X
    Keywords: optical emission spectroscopy ; cascade arc ; surface modification ; fluorination ; plasma polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical Emission Spectroscopy (OES) was used to identify reactive species and their excitation states in low-temperature cascade arc plasmas of N2, CF4, C2F4, CH4, and CH3OH. In a cascade arc plasma, the plasma gas (argon or helium) was excited in the cascade arc generator and injected into a reactor in vacuum. A reactive gas was injected into the cascade arc torch (CAT) that was expanding in the reactor. What kind of species of a reactive gas, for example, nitrogen, are created in the reactor is dependent on the electronic energy levels of the plasma gas in the cascade arc plasma jet. OES revealed that no ion of nitrogen was found when argon was used as the plasma gas of which metastable species had energy less than the ionization energy of nitrogen. When helium was used, ions of nitrogen were found. While OES is a powerful tool to identify the products of the cascade arc generation (activation process), it is less useful to identify the reactive species that are responsible for surface modification of polymers and also for plasma polymerization. The plasma surface modification and plasma polymerization are deactivation processes that cannot be identified by photoemission, which is also a deactivation process. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1583-1592, 1998
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    Unbridged bivalent lanthanidocenes for isotactic and stereomultiblock polymerization of methyl methacrylate (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1599-1606 
    Details
    ISSN: 0887-624X
    Keywords: bivalent organolanthanides ; polymerization ; methyl methacrylate ; stereomultiblock polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bivalent organolanthanides with unbridged substituted indenyl or fluorenyl ligands (1-SiMe3Ind)2YTHF (I), (9-SiMe3Flu)2YTHF (II), were found to efficiently catalyze the stereoregular polymerization of methyl methacrylate. The microstructure of resultant polymers was shown to be dependent of a conformation that the ligands adopt at the polymerization temperature. The formation of isotactic rich PMMAs from complex II was proposed to be associated with the fluctuation of the 9-trimethylsilylfluorenyls around a C2 symmetric twisted-conformation. The formation of the multi(syndioPMMA-block-iso-PMMA) polymers from the mixture of rac- and meso-isomers of I was rationalized on the basis of competing conjugate addition and inversion of the metallocene conformation. Surprisingly, both rac- and meso-isomers of I were found to operate with similar activity and stereospecifity, although the stereospecific operation of the meso-form was not completely understandable. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1599-1606, 1998
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    Investigation of the microstructure of metallocene-catalyzed norbornene-ethylene copolymers using NMR spectroscopy (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1633-1638 
    Details
    ISSN: 0887-624X
    Keywords: cyclic olefin copolymers ; norbornene ; metallocene catalysts ; NMR ; microstructure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Norbornene-ethylene copolymers were prepared using the metallocene catalyst ethylene bis (indenyl) zirconium dichloride with MAO, and their microstructure was characterized with 1H-NMR and 13C-NMR methods. From a Cosy 1H-NMR spectrum it was found that all norbornene units are enchained in the exo-configuration. The sequence distribution of norbornene units was investigated using 13C-1H correlations, hmqc for one-bond correlations, and hmbc for two- or three-bond correlations. It was shown that norbornene diads were formed at a high norbornene content (45 mol %). When further increasing the norbornene incorporation (66 mol %) a number of new signals were obtained. A Cosy 1H-NMR spectrum revealed a new crosspeak which, according to the corresponding 13C-NMR shifts (hmqc), correlated well with a terminal unit of a trimer of norbornene. This means that at very high norbornene contents, norbornene triads can be formed. Because the formation of isotactic norbornene triads is very difficult to understand from a sterical point of view, an epimerization process causing stereoirregularities in the norbornene triad is proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1633-1638, 1998
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    Syntheses and biological activities of α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil and its polymers (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1625-1632 
    Details
    ISSN: 0887-624X
    Keywords: α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (MMTFU) ; poly(MMTFU-co-AA) ; poly(MMTFU-co-VAc) ; photopolymerization ; average molecular weight ; in vitro cytotoxicity ; in vivo antitumor activity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new monomer, α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil (MMTFU), was synthesized from 5-fluorouracil (5-FU) and α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl chloride (MMTC). Poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil) [poly(MMTFU)], poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-acrylicco-AA), and poly(α-methoxy-3,6-endo-methylene-1,2,3,6-tetrahydrophthaloyl-5-fluorouracil-co-vinyl acetate) [poly(MMTFU-co-VAc)] were synthesized by photopolymerizations using 2,2-dimethoxy-2-phenylacetophenone (DMP) as the photoinitiator. The synthesized MMTFU and the polymers were identified by FT-IR, 1H-NMR, and 13C-NMR spectroscopies. The contents of MMTFU in poly(MMTFU-co-AA) and poly(MMTFU-co-VAc) determined by elemental analysis were 63 and 57 mol %, respectively. The number average molecular weights and polydispersity indices of synthesized polymers determined with GPC were in range of 7,700-19,100 and 1.6-2.7. The in vitro cytotoxicities of samples were evaluated with mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line. The cytotoxicities of 5-FU and synthesized samples against cancer cell lines increased in following orders: 5-FU 〉 MMTFU 〉 poly(MMTFU) 〉 poly(MMTFU-co-AA) 〉 poly(MMTFU-co-VAc). The in vivo antitumor activities of the synthesized samples against mice bearing the sarcoma 180 tumor cell line were evaluated. The in vivo antitumor activities of the polymers were greater than that of 5-FU at a dose of 80 mg/kg. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1625-1632, 1998
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    Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of 2-hydroxyethyl acrylate (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1417-1424 
    Details
    ISSN: 0887-624X
    Keywords: 2-hydroxyethyl acrylate ; poly(2-hydroxyethyl acrylate) ; atom transfer radical polymerization (ATRP) ; controlled free radical polymerization ; MALDI-MS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of atom transfer radical polymerization (ATRP) to the homopolymerization of 2-hydroxyethyl acrylate, a functional monomer, is reported. The polymerizations exhibit first-order kinetics, and molecular weights increase linearly with conversion. Polydispersities remain low throughout the polymerization (Mw/Mn ≈ 1.2). Reactions were conducted in bulk and in 1 : 1 (by volume) aqueous solution; the latter demonstrates the resilience of ATRP to protic media. Analysis of poly(2-hydroxyethyl acrylate) by MALDI-MS and 1H-NMR shows Mn,exp to be much closer to Mn,th than those observed by SEC using polystyrene standards. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1417-1424, 1998
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    Hyperbranched polymers 10 years after (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1685-1698 
    Details
    ISSN: 0887-624X
    Keywords: hyperbranched polymer ; dendrimers ; comb-burst dendrimers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been about 10 years since the first intentional preparation of hyperbranched polymer was disclosed. Hyperbranched polymers, as well as dendrimers, may find utilities in the areas where the structural uniqueness of these polymers gives merit. There has been much progress in the structural understanding and the methods of synthesis of these polymers. However, functional understanding and utility of these polymers are still in infancy. Better understanding on physical properties of these polymers, such as solubility and miscibility of these polymers in solvents or with polymers, and functional group dependency to the thermal relaxation process are needed for further development of the subject. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A: Polym. Chem. 36: 1685-1698, 1998
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    Copolymerization of dienes with neodymium tricarboxylate-based catalysts and cis-polymerization mechanism of dienes (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1707-1716 
    Details
    ISSN: 0887-624X
    Keywords: neodymium tricarboxylate ; cis-poly (2,3-dimethylbutadiene) ; copolymerization of dienes ; cis-1,4 polymerization mechanism ; back-biting coordination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that poly(butadiene), poly(isoprene), and poly(2,3-dimethylbutadiene) with high cis-1,4 content were obtained with Nd(OCOR)3-(i-Bu)3Al-Et2AlCl catalysts (R = CF3, CCl3, CHCl2, CH2Cl, CH3) in hexane at 50°C [cis-1,4 content: poly(BD), 〉 98%; poly(IP), ≥ 96%; poly(DMBD), ≥ 94%]. Copolymerization of IP and styrene (St) was carried out at various monomer feed ratios to evaluate the monomer reactivity ratio and cis-1,4 content of the diene unit and then to elucidate the cis-1,4 polymerization mechanism of IP. The cis-1,4 content of the IP unit in the copolymers decreased with increasing St content in the copolymers. The cis-1,4 polymerization was disturbed by incorporating St unit in the copolymers, since the penultimate St unit hardly coordinates to the neodymium metal, resulting in a decrease of the cis-1,4 content in the copolymers. That is, the cis-1,4 polymerization of IP is suggested to be controlled by a back-biting coordination of the penultimate diene unit. On the other hand, in the case of poly(BD-co-IP) and poly(BD-co-DMBD), the cis-1,4 content of the BD, IP, and DMBD units in the copolymers was almost constant (cis: 94-98%), irrespective of the monomer feed ratios and polymerization temperature. Consequently, the penultimate IP and DMBD units favorably control the terminal BD, IP, or DMBD unit to the cis-1,4 configuration through the back-biting coordination. For the monomer reactivity ratios, a clear difference was observed in each system: rBD = 1.22, rIP = 1.14; rBD = 40.9, rDMBD = 0.15. Low polymerizability of DMBD was mainly ascribed to the steric effect of the methyl substituents. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1707-1716, 1998
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    Microstructure effect in the coupling reactions of polymeric organolithium compounds using chlorosilanes (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1743-1753 
    Details
    ISSN: 0887-624X
    Keywords: coupling reaction ; living polymer ; microstructure ; coupling yield ; 1,4-enchainment ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The most important variable affecting the yield in the coupling reactions of polymeric organolithium compounds with chlorosilane compounds has been investigated through size-exclusion chromatographic (SEC) analysis. The coupling reaction of poly(styryl)lithium with dichlorodimethylsilane as a silane-coupling agent provided 44 wt % of the coupling yield. The coupling yield, depending on the chain end reactivity of active polymers, was not greatly affected. The addition of a Lewis base such as N,N,N′,N′-tetramethylethylenediamine (TMEDA) even after complete polymerization of the dienes in hydrocarbon seems to affect the coupling reaction, resulting in decreasing the yield. The 1,2- or 3,4-enchain contents in the polydiene backbones affected the reduction of the linking efficiency in the coupling of the poly(dienyl)lithiums with chlorosilanes as the linking agent. The linking yields of the active polymers including over 75 mol % of 1,2- or 3,4-enchainment on the polydiene segment were below 20 wt %. The linking yields exhibited a dependence not only on the steric requirement of the chain end, but also the microstructure of the polydiene segment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1743-1753, 1998
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    Synthesis and properties of novel polymers having S-methyldibenzothiophenium salt moieties (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1779-1784 
    Details
    ISSN: 0887-624X
    Keywords: poly(sulfonium salt) ; poly(2-vinyldibenzothiophene) ; 5-methyl-2-vinyldibenzothiophenium tetrafluoroborate ; sulfonium monomer ; radical polymerization ; polymer reaction ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A polymer having dibenzothiophenium salt moieties [poly(sulfonium salt), 2] was prepared by the reaction of poly(2-vinyldibenzothiophene) (1) with CH3I and AgBF4 in CH2ClCH2Cl at room temperature for 24 h. The obtained polymer 2 was found to contain 71% of the methyldibenzothiophenium tetrafluoroborate unit. A monomer carrying the sulfonium salt moiety, i.e., 5-methyl-2-vinyldibenzothiophenium tetrafluoroborate (4), was independently prepared and subjected to radical polymerization to give a polymer (5) in 88% yield (methyldibenzothiophenium tetrafluoroborate unit: 79%). The thermal decompositions of 2 and 5 took place in two steps; the first step involved the formation of polymer 1 by demethylation. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1779-1784, 1998
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    Influence of plasma treatment on the molar mass of poly(ethylene terephthalate) investigated by different chromatographic and spectroscopic methods (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1639-1648 
    Details
    ISSN: 0887-624X
    Keywords: poly(ethylene terephthalate) (PET) ; plasma ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of different types of low and atmospheric pressure plasma on poly(ethylene terephthalate) (PET) has been studied in terms of changes in molar mass and molar mass distribution. Apart from a variation of plasma gases (oxygen, helium) different types of plasma (microwave, radio frequency, corona discharge) were used for the plasma surface modification. The changes in molar mass and types of functional end groups of lower molar mass products were investigated by means of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOFMS), whereas the high-molar mass fraction was analyzed by means of size-exclusion chromatography (SEC). The formation of crosslinked products during exposure to a helium plasma, which emits preponderately energy-rich and intense ultraviolet radiation, was proved by means of thermal field-flow fractionation (ThFFF). This method combined with a multiangle laser light scattering (MALLS) detector allows detection of weakly crosslinked polymers and microgels. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1639-1648, 1998
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    Synthesis and characterization of poly(benzobisthiazole) with tetramethylbiphenyl moiety in the main chain (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1407-1416 
    Details
    ISSN: 0887-624X
    Keywords: PBZT ; polycondensation ; tetramethylbiphenyl substituted ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(benzobisthiazole)s containing an ortho-tetramethyl substituted biphenyl moiety were synthesized via the polycondensation of 2,5-diamino-1,4-benzenedithiol dihydrochloride with 2,2′,6,6′-tetramethylbiphenyl-4,4′-dicarboxylic acid in poly(phosphoric acid) (PPA). The intrinsic viscosities of the tetramethylbiphenyl poly-(benzobisthiazole)s in chlorosulfonic acid at 30°C were in the range of 6.9-13.4 dL/g. Copolycondensation of 2,5-diamino-1,4-benzenedithiol dihydrochloride with terephthalic acid and 2,2′,6,6′-tetramethylbiphenyl-4,4′-dicarboxylic acid was carried out as well by varying the ratio of the two dicarboxylic acid monomers in the reactant mixture. The homopolymers and copolymers were characterized by Fourier transform infrared spectroscopy (FTIR) and 13C solid-state nuclear magnetic resonance spectroscopy (NMR). Thermal stability of the polymers was evaluated by thermogravimetric analysis (TGA) and thermogravimetric mass spectrum analysis (TG-MS). The tetramethylbiphenyl poly(benzobisthiazole)s were found to be more stable at elevated temperatures than the parent poly(p-phenylene benzobisthiazole) (PBZT). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1407-1416, 1998
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    Novel aromatic polyhydrazides and poly(amide-hydrazide)s based on “multiring” flexible dicarboxylic acids (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1847-1854 
    Details
    ISSN: 0887-624X
    Keywords: polyhydrazides ; poly-1,3,4-oxadiazoles ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two flexible dicarboxylic acid monomers, 4,4′-[isopropylidenebis(1,4-phenylene)dioxy]dibenzoic acid (1) and 4,4′-[hexafluoroisopropylidenebis(1,4-phenylene)-dioxy]dibenzoic acid (3), were synthesized from readily available compounds in two steps in high yields. High molecular-weight polyhydrazides and poly(amide-hydra-zide)s were directly prepared from dicarboxylic acids 1 and 3 with terephthalic dihydrazide (5), isophthalic dihydrazide (6), and p-aminobenzhydrazide (7) by the phosphorylation reaction by means of diphenyl phosphite (DPP) and pyridine in N-methyl-2-pyrrolidone (NMP)/LiCl, or prepared from the diacyl chlorides of 1 and 3 with the hydrazide monomers 5-7 by the low-temperature solution polycondensation in NMP/LiCl. Less favorable results were obtained when using triphenyl phosphite (TPP) instead of DPP in the direct polycondensation reactions. Except for those derived from terephthalic dihydrazide, the resulting polyhydrazides and poly(amide-hydrazide)s could be cast into colorless, flexible, and tough films with good tensile strengths. All the hydrazide polymers and copolymers are amorphous in nature and are readily soluble in various polar solvents such as NMP and dimethyl sulfoxide (DMSO). Their Tgs were recorded in the range of 162-198°C and could be thermally cyclodehydrated into the corresponding polyoxadiazoles and poly(amide-oxadiazole)s approximately in the region of 300-380°C, as evidenced by the DSC thermograms. The oxadiazole polymers and copolymers showed a dramatically decreased solubility and higher Tg when compared to their respective hydrazide prepolymers. They exhibited Tgs of 190-216°C and were stable up to 450°C in air or nitrogen. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1847-1854, 1998
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    Novel polyisobutylene/poly(dimethylsiloxane) bicomponent networks. I. Synthesis and characterization (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1891-1899 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; poly(dimethylsiloxane) ; hydrosilation ; bicomponent networks ; molecular weight between crosslinks ; network functionality ; sol fraction ; extractables ; model networks ; end-linking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks is described. The synthesis strategy (see Figure 1) was to prepare well-defined and -characterized allyl-tritelechelic polyisobutylenes [φ(PIB - C - C=C)3] and SiH-ditelechelic poly(dimethylsiloxanes) (HSi-PDMS-SiH) and then crosslink these moieties by hydrosilation. The φ(PIB - C - C=C)3 was prepared by living isobutylene polymerization followed by end-quenching with allyltrimethylsilane, whereas the HSi-PDMS-SiH was obtained by equilibrium polymerization of octamethylcyclotetrasiloxane and tetramethyldisiloxane. The detailed structures of the starting polymers were characterized by GPC and 1H-NMR spectroscopy. A series of PIB/PDMS bicomponent networks of varying compositions and average molecular weights between crosslinks (Mc) of ∼ 20,000 g/mol were assembled. Optimum crosslinking conditions were defined in terms of H2PtCl6 catalyst concentration, nature of solvent, time, temperature, and stoichiometry of ∼ CH2CH=CH2/∼SiH groups, allowing for the convenient synthesis of well-defined model bicomponent networks. Swelling studies and elemental analysis confirm the correctness of the synthetic strategy. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1891-1899, 1998
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    Novel polyisobutylene/poly(dimethylsiloxane) bicomponent networks. II. Network structure and property characterization (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1901-1910 
    Details
    ISSN: 0887-624X
    Keywords: polyisobutylene ; poly(dimethylsiloxane) ; bicomponent networks ; network structure ; molecular weight between crosslinks ; network properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first part of this series concerned the synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks; the present paper concerns the structure and property characterization of a series of bicomponent networks of varying compositions (PIB wt %/PDMS wt % = 92/8, 70/30, 50/50, 35/65) having average molecular weights between crosslinks (Mc) of ˜ 20,000 g/mol. According to network structure analysis by uniaxial equilibrium stress-strain measurements, the experimental Mc's are in excellent agreement with theoretical values. Hydrosilation end-linking efficiency was quantitated by the amount of sol and functional group analysis by 1H-NMR spectroscopy. NMR evidence indicates double-bond isomerization during hydrosilation. Network compositions by elemental analysis together with the low sol fractions indicate efficient crosslinking. These data suggest highly efficient network formation and well-defined bicomponent network structures. While PIB and PDMS showed Tg's at -72 and -124°C, respectively, the bicomponent network did not exhibit clearly discernible phase transitions. The heat stability of bicomponent networks increased slightly with increasing PDMS content showing initial (10%) degradation temperatures at ˜ 380°C in nitrogen and ˜ 320°C in air. Tensile strengths and elongations were dependent on composition and varied in the 0.6-3.8 MPa and 600-1100% ranges, respectively. The swelling behavior was not much affected by composition. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1901-1910, 1998
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    Synthesis of aromatic polyesters and polyamides by alternating copolymerizations of 1,4-dicarbonyl-1,4-dihydronaphthalene with bezoquinones and benzoquinone diimines (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1929-1936 
    Details
    ISSN: 0887-624X
    Keywords: aromatic bisketene ; aromatic polyesters ; aromatic polyamides ; addition reaction ; benzoquinones ; benzoquinone diimines ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,4-Dicarbonyl-1,4-dihydronaphthalene (1) was synthesized by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride with triethylamine and obtained as its very dilute solution, but it easily polymerized in the concentration as high as 0.1 mol/L to give its polymer. 1 generated in situ by the dehydrochlorination reaction of 1,4-dihydronaphthalene-1,4-dicarbonyl chloride in a deoxygenated toluene polymerized alternatingly with benzoquinones such as 2-dodecylthio-p-benzoquinone, 2,5-di(tert-butyl)-p-benzoquinone, p-benzoquinone, and 2,3-dichloro-5,6-dicyano-p-benzoquinone, and with benzoquinone diimines such as N,N′-diethoxycarbonyl-p-benzoquinone diimine, N,N′-dibenzoyl-p-benzoquinone diimine, and N,N′-diphenyl-p-benzoquinone diimine to give aromatic polyesters and polyamides, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1929-1936, 1998
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    Polymerization of epoxide by a fluorenyltriphenylphosphonium salt as a thermally latent initiator (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1957-1960 
    Details
    ISSN: 0887-624X
    Keywords: cationic polymerization ; thermally latent initiator ; fluorenyltriphenylphosphonium salt ; epoxide ; glycidyl phenyl ether ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    Aminolysis kinetics of model and polymer-bound anhydride moieties in low- and high-viscosity media (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1573-1582 
    Details
    ISSN: 0887-624X
    Keywords: amic acid ; secondary amine ; maleic anhydride ; melt reaction kinetics ; model compounds ; polymer-bound functional groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study examines the legitimacy of using the reaction kinetics of low molecular weight model compounds in solution to predict the chemical kinetics of polymer-bound species in a homogeneous melt. The reaction under study takes place between an aliphatic secondary amine, diisooctadecylamine (DiOA), and a 5-membered anhydride ring, saturated maleic anhydride (MA), forming an amic acid product. The MA species was present as a pendant graft on either a model compound, dodecane-g-(maleic anhydride) (dodecane-g-MA), or a polymer chain, linear low-density polyethylene-g-(maleic anhydride) (LLDPE-g-MA). Pseudo-second-order kinetics of the anhydride consumption are followed by infrared spectroscopy, either in situ in dodecane solution or by scanning frozen film samples taken from a linear low-density polyethylene melt. It was found that the LLDPE-g-MA/DiOA system reacted at a slightly slower rate than the dodecane-g-MA/DiOA system in the low-viscosity solution at 140°C. In the melt, the dodecane-g-MA/DiOA system experienced a small decrease in the overall reaction rate compared to the same reaction carried out in dodecane. However, the LLDPE-g-MA/DiOA system underwent a 65% decrease in the observed second-order rate constant on going from a solution to the melt. To explain these phenomena, the effects of diffusion, miscibility, and chain entanglements in the melt are examined here. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1573-1582, 1998
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    On-line monitoring, modeling, and model validation of semibatch emulsion polymerization in an automated reactor control facility (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1553-1571 
    Details
    ISSN: 0887-624X
    Keywords: seeded emulsion polymerization ; gel effect ; radical entry ; particle size sensor ; semibatch model ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The modeling of the semibatch emulsion polymerization of styrene and its validation against data obtained from a reactor facility is presented. The model, which describes the growth of a monodisperse polystyrene seed as neat monomer is fed to the reactor, incorporates recent findings in radical diffusion and kinetics. The current controversy surrounding radical absorption into particles is handled by considering absorption via propagation, diffusion, and collision in the model. Simulation results including weight fraction polymer inside the particles and particle diameter are compared to data obtained from a custom-designed and built automated reactor control facility capable of on-line density and on-line particle diameter measurements. Good agreement between simulation results and experimental data are obtained for any of the three absorption mechanisms considered by varying only one adjustable parameter located in the absorption rate coefficient relation. A sensitivity analysis of the model to this adjustable parameter, using the program ODESSA, is also presented and shown to be an important tool in the validation procedure. Lastly, an analysis of the dynamics of the process shows the variety of phenomena that can be obtained in a semibatch reactor including regions that exhibit pseudosteady states, autoacceleration of the rate, and limiting conversion. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1553-1571, 1998
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    Synthesis of poly(styrene-b-tetrahydrofuran-b-styrene) triblock copolymers by transformation from living cationic into living radical polymerization using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a transforming agent (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2059-2068 
    Details
    ISSN: 0887-624X
    Keywords: poly(THF) ; TEMPO ; both the chain ends ; triblock copolymer ; living radical polymerization ; a transforming agent ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of poly(styrene-b-tetrahydrofuran (THF)-b-styrene) triblock copolymers was performed by transformation from living cationic into living radical polymerization, using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO) as a transforming agent. Sodium 4-oxy-TEMPO, derived from 4-hydroxy-TEMPO, reacted with the living poly(THF), which was prepared by cationic polymerization of THF using trifluoromethanesulfonic acid anhydride as an initiator, resulting in quantitative formation of the poly(THF) with TEMPO at both the chain ends. The resulting polymers were able to serve as a polymeric counter radical for the radical polymerization of styrene by benzoyl peroxide, to give the corresponding triblock copolymer in quantitative efficiency. The polymerization was found to proceed in accordance with a living mechanism, because the conversion of styrene linearly increased over time, and the molar ratio of styrene to THF units in the copolymer also increased as a result of increasing the conversion. The TEM pictures demonstrated that the resulting copolymers promoted microphase segregation. It was found that the films of these copolymers showed contact angles intermediate between those of poly(THF) and of polystyrene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2059-2068, 1998
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    Surface functionalization of polymer latex particles. III. A convenient method of producing ultrafine poly(methylstyrene) latexes with aldehyde groups on the surface (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2103-2109 
    Details
    ISSN: 0887-624X
    Keywords: functionalization of polymer latexes ; poly(methylstyrene) ; catalytic oxidation ; ultrafine particles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A convenient method of preparing ultrafine poly(methylstyrene) (PMS) latex particles with aldehyde groups on the surface is developed. PMS latexes in the size range 33-81 nm were prepared via microemulsion polymerization, using cetyltrimethylammonium bromide (CTAB) as surfactant. The surface of the PMS latexes was oxidized in the presence of tert-butyl hydroperoxide catalyzed by copper(II) chloride. As the degree of oxidation increased up to 6 h, the amounts of aldehyde group increased. Bigger particles were found to have a slightly higher rate of oxidation than small ones under the same oxidation conditions. The particle size underwent little change during oxidation; thus, the amounts of functional groups and the particle size could be controlled concurrently. Dialysis study of the oxidized PMS microlatexes indicated that the instability of highly oxidized PMS microlatexes was caused by the reduction of total surface charge density due to the presence of carboxylic acid groups. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2103-2109, 1998
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    New synthetic route for weak base anion exchangers based on crosslinked polystyrene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2151-2154 
    Details
    ISSN: 0887-624X
    Keywords: anion exchangers ; crosslinked polystyrene ; Friedel-Crafts acetylation ; Mannich amination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Helix-sense-selective copolymerization of phenyl[bis(2-pyridyl)]methyl methacrylate, diphenyl(2-pyridyl)methyl methacrylate and triphenylmethyl methacrylate with chiral anionic initiators (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2127-2133 
    Details
    ISSN: 0887-624X
    Keywords: phenyl[bis(2-pyridyl)]methyl methacrylate ; (S)-(+)-1-(2-pyrrolidinylmethyl)pyridine ; anionic asymmetric copolymerization ; optically active copolymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically active poly[triphenylmethyl methacrylate-co-phenyl[bis(2-pyridyl)]methyl methacrylate] (poly[TrMA-co-PB2PyMA], poly[diphenyl(2-pyridyl)methyl methacrylate-co-phenyl[bis(2-pyridyl)]methyl methacrylate] (poly[D2PyMA-co-PB2PyMA]), and poly[triphenylmethyl methacrylate-co-diphenyl(2-pyridyl)-methyl methacrylate] (poly[TrMA-co-D2PyMA]) were prepared by helix-sense-selective copolymerization with complexes of organolithium with (-)-sparteine [(-)Sp],(S, S)-(+)- and (R, R)-(-)-2,3-dimethoxy-1,4-bis(dimethylamino)butane [(+)- and (-)DDB], and (S)-(+)-2-(1-pyrrolidinylmethyl)pyridine [(+)PMP] as anionic initiators in toluene at low temperature. The copolymers obtained with (-)Sp and (+)DDB or (-)DDB complexes of organolithium showed low optical activity, but to [(+)PMP] complex with N,N′-diphenyleneamine monolithium amide [(+)PMP-DPEDA-Li)] was effective in synthesizing copolymers of high optical rotation ([α]25D about +320 to + 370°) which were comparable to those of corresponding homopolymers with one-handed helical structure. The optical rotations of poly[TrMA-co-PB2PyMA] and poly[TrMA-co-D2PyMA] were much more stable than that of poly(D2PyMA) or poly(PB2PyMA) in a solution of CHCl3-2,2,2-trifluoroethanol (10 : 1, v/v) at 25°C, but optical rotation of poly[D2PyMA-co-PB2PyMA] slowly decreased with time in the same conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2127-2133, 1998
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    Preparation of poly(aryleneethynylene)-type copolymers containing flexible linking methylene units. Optical properties of the copolymers suggesting occurrence of energy transfer between π-conjugated local units (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2201-2207 
    Details
    ISSN: 0887-624X
    Keywords: poly(aryleneethynylene) ; palladium-catalyzed ; copolymer ; optical properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Palladium-catalyzed polycondensation between 2,5-diiodo-3-hexylthiophene I-Th(Hex)-I with mixtures of p-diethynylbenzene HC≡C - Ph - C≡CH and α,ω-diethynylalkane HC≡C(CH2)lC≡CH (l = 3 or 8) gives poly(aryleneethynylene) PAE-type copolymers [C≡C(CH2)lC≡C - Th(Hex)]m[C≡C - Ph - C≡C - Th(Hex)]n containing the methylene unit. The copolymers have a molecular weight (Mn) of about 1.2 × 104 as determined by GPC (polystyrene standard) and are considered to possess essentially a random sequences in view of the  - C≡C(CH2)lC≡C -  and  - C≡C - Ph - C≡C -  units as judged from their UV-visible spectra. By the incorporation of the (CH2)l unit, the λmax position of the corresponding PAE homopolymer [C≡C - Ph - C≡C - Th(Hex)]n is shifted to a shorter wavelength. However, the copolymers give rise to a photoluminescence PL peak essentially agreeing with a PL peak of the homopolymer, suggesting occurrence of energy transfer in the copolymer. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2201-2207, 1998
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    Photolysis of a fluorinated polymer film by vacuum ultraviolet radiation (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2215-2222 
    Details
    ISSN: 0887-624X
    Keywords: fluorinated polymer ; vacuum ultraviolet ; Xe lamp ; photolysis ; photo-oxidation ; surface modification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the photolysis of a fluoroethylene-fluoropropylene copolymer (FEP) film by vacuum ultraviolet (VUV) radiation from a resonance Xe lamp at a wavelength of 147 nm and air pressures of 0.05 and 2.5 Torr. The chemical changes in the FEP surface layer were investigated by Fourier-transform infrared spectroscopy with attenuated total reflection attachment and X-ray photoelectron spectroscopy. Double bonds were found to be the main product in the case of VUV treatment at 0.05 Torr, while photo-oxidation of FEP occurred predominantly by VUV treatment at 2.5 Torr under formation of the  - CF2C(O)F group. This oxygen-containing group was more effectively formed in the FEP surface layer by VUV photo-oxidation than by conventional surface oxidation techniques such as treatments by plasma and corona discharge and ozone. Storage of the VUV-treated polymers in air at 50% relative humidity resulted in hydrolysis of  - CF2C(O)F to the  - CF2COOH group. Substantial improvement of the film wettability was noticed after VUV photo-oxidation. These findings suggest that VUV irradiation provides a high potential for surface modification of fluorinated polymers which are known to be particularly resistant against functionalization by conventional surface modification techniques such as plasma treatment. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2215-2222, 1998
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    A positive-working photosensitive alkaline-developable polyimide with a highly dimensional stability and low dielectric constant based on poly(amic acid) as a polyimide precursor and diazonaphthoquinone as a photosensitive compound (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2261-2267 
    Details
    ISSN: 0887-624X
    Keywords: photosensitive polyimide ; highly dimensional stability ; low dielectric constant ; poly(amic acid) ; diazonaphthoquinone ; positive type ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A positive-working photosensitive polyimide precursor based on fluorinated poly(amic acid) (FPAA) and 2,3,4-tris(1-oxo-2-diazonaphthoquinon-4-ylsulfonyloxy)benzophenone (D4SB) as a photosensitive compound has been developed. FPAA was prepared by ring-opening polyaddition of dianhydrides, pyromellitic dianhydride and biphenyltetracarboxylic dianhydride, with diamine, 2,2′-bis(trifluoromethyl)benzidine, in methanol. The FPAA film showed excellent transparency to UV light and good solubility in a wide range of organic solvents. The dissolution behavior of FPAA containing 30 wt % D4SB after exposure was studied, and it was found that the difference of dissolution rate between exposed and unexposed parts was enough to get high contrast due to the photochemical reaction of D4SB in the polymer film. The photosensitive fluorinated polyimide (FPI) precursor containing 30 wt % D4SB showed a sensitivity of 80 mJ cm-2 and a contrast of 7.8 with 365 nm light when it was developed with 0.3% aqueous tetramethyl ammonium hydroxide solution at room temperature. The FPI film cured up to 360°C had a low coefficient of thermal expansion of 10.3 ppm °C-1 and a low dielectric constant of 3.04. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2261-2267, 1998
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    Synthesis and characterization of new poly(amide-imide)s from 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene with various diamines (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2301-2307 
    Details
    ISSN: 0887-624X
    Keywords: 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene (BTTB) ; direct polycondensation ; poly(amide-imide)s ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New poly(amide-imide)s were prepared from a diimide-dicarboxylic acid, 1,4-bis(4-trimellitimidophenoxy)-2-tert-butylbenzene (BTTB), with various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. The new diimide-dicarboxylic acid BTTB containing an ether linkage and tert-butyl substituent was synthesized by the condensation reaction of 1,4-bis(4-aminophenoxy)-2-tert-butylbenzene with trimellitic anhydride. All the polymers were obtained in quantitative yields with inherent viscosities of 0.62-1.06 dL g-1. The polymers were amorphous, and most of them were readily soluble in aprotic polar solvents such as NMP, N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF), as well as in less polar solvents such as dimethyl sulfoxide (DMSO), m-cresol, pyridine, and γ-butyrolactone, and also even in tetrahydrofuran. The glass transition temperatures of the polymers were determined by DSC method, and they were in the range of 238-279°C. These polymers were stable up to 408-449°C in air and 451-483°C in nitrogen and lose 10% weight in the range of 479-525°C in air and 480-528°C in nitrogen atmosphere. The polymer films had a tensile strength range of 71-115 MPa, an elongation at break range of 4-14%, and a tensile modulus range of 2.3-3.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2301-2307, 1998
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    Synthesis and surface characterization of heparin-immobilized polyetherurethanes (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2331-2338 
    Details
    ISSN: 0887-624X
    Keywords: poly(ether urethane) ; surface modification ; heparin immobilization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel poly(ether urethanes) containing diester groups in the side chains (PU) were synthesized from 4,4′-diphenylmethyl diisocyanate, polytetramethylene glycol, and diethyl bis(hydroxymethyl)malonate as a chain extender. The surface modification of the PU film was carried out by a hydrolysis reaction, poly(ethylene oxide) (PEO) grafting, and heparin immobilization, and the surface-modified PUs were then characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), and a contact angle goniometer. The concentration of carboxylic acid groups introduced on the PU surfaces as determined by the rhodamine interaction method was 61 nmol/cm2 when treated with 4N NaOH/methanol (1 : 2 v/v) for 30 min and subsequently with a citric acid-methanolic aqueous solution. The amounts of heparin coupled to the carboxyl groups on the PU surfaces and to the terminus amino groups on the PU-PEO were 0.92 and 0.84 μ g/cm2, respectively. There was almost no heparin released from the immobilized surface of a physiological solution for 100 h, thereby indicating the strong stability of immobilized heparin. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2331-2338, 1998
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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