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  • Chemistry  (114,948)
  • Chemical Engineering  (6,730)
  • 1995-1999  (38,453)
  • 1980-1984  (33,715)
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  • 101
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    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1941-1942 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 102
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1957-1967 
    ISSN: 0887-624X
    Keywords: end-capping reactions ; oligo(styryl)lithium anions ; gas chromatography ; mass spectrometry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anionic living polymerization methods, using organometallic initiators such as butyllithium reagents, have proven useful for, inter alia, styrene polymerization and are amenable to subsequent functionalization of poly(styryl)lithium in the termination step. In this study, general methods for the selective preparation of small styrene oligomers and termination of the intermediate oligo(styryl)lithium anions were investigated. The crude reaction mixtures were analyzed directly by tandem gas chromatography/mass spectrometry (GC/MS). Of the carbon- and silicon-based electrophiles tested, chloro(chloroalkyl)silanes, Cl-SiR2(CH2)nCl in particular, were shown by GC/MS to be regioselective end-capping reagents, thus allowing subsequent transformation to the primary amine. The combined GC/MS data allow not only an estimate of the degree of functionalization, but also the identification of by-products, thus providing insight into the end-capping process that otherwise might be difficult to access. © 1995 John Wiley & Sons, Inc.
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  • 103
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1987-1994 
    ISSN: 0887-624X
    Keywords: aromatic polyamides ; polyisophthalalamides ; pendent oligomeric benzamide groups ; 5-(4-benzoylamino-1-benzoylamino)isophthalic acid ; water uptake ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyisophthalamides having pendent oligomeric benzamide groups were prepared by the Yamazaki reaction from common aromatic diamines and 5-(4-benzoylamino-1-benzoylamino)isophthalic acid. The latter was synthesized from 5-aminoisophthalic acid in a three-step synthesis by successive incorporation of benzamido groups. The new polymers were characterized by NMR, DSC, TGA, and WAXD and the properties were compared to those of corresponding unsubstituted polyisophthalamides. All of the polymers were essentially amorphous and their Tgs were about 20°C higher than the reference polymers. Initial thermal decomposition temperatures ranged from 375 to 420°C. All of the polymers were soluble in aprotic polar solvents without added salts. Properties of particular note were: the water uptake, which was particularly high, ranging from 7.5 to 18.2%, and the temporary insolubilization in concentrated sulfuric acid of films of the polymers heated for a short time to ≥ 200°C. © 1995 John Wiley & Sons, Inc.
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  • 104
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2049-2055 
    ISSN: 0887-624X
    Keywords: graft polymerization ; grafting rate ; electron beam irradiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: LLDPE film pre-irradiated by electron beam (EB) in air and argon was grafted in an aqueous acrylamide solution containing Mohr's salt in the concentration range 0.0025-2% The grafting rate and yield were strongly dependent on the Mohr's salt concentration, mainly as a result of chain termination. The exponential grafting rate dependence on the pre-irradiation dose was quite insensitive to a hundred-fold variation in Mohr's salt concentration. © 1995 John Wiley & Sons, Inc.
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  • 105
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2157-2163 
    ISSN: 0887-624X
    Keywords: reactive polyester ; pendant carboxyl group ; chemoselective polycondensation ; polymer catalyst ; polymer reaction ; bifunctional catalytic mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polyester, copolyester, and poly(ester-amide-thioester) having pendant carboxyl groups are directly synthesized by the organic phase/water phase interfacial polyconden-sation using low-molecular and polymeric phase transfer catalysts. Spectral analysis of the resulting polymers indicates that the nucleophilicity of salts of phenols to diacid chloride is far higher than that of salts of carboxylic acids and chemoselective esterification occurs in a 100% yield. Even if the polymeric catalyst having amino acid moiety as a nucleophilic group is used in the polycondensation, the polymers do not contain anhydride groups. The polyester can be almost quantitatively converted to polymers with different reactive groups by reacting the pendant carboxyl groups with alkyl halides in a DMAc-H2O mixture con-taining K2CO3. A bifunctional catalytic mechanism is proposed for the chemical modification of the polyesters. © 1995 John Wiley & Sons, Inc.
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  • 106
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2175-2182 
    ISSN: 0887-624X
    Keywords: gadolinium tricarboxylate ; copolymerization of butadiene and styrene ; effect of pKa of ligand ; diad analysis ; cis polymerization mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)3: R = CH3, CH2Cl, CHCl2, CCl3, and CF3], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)3 - (i - Bu)3Al - Et2AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97-99%) in 22-85% yields for 2-24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)3: CF3 〉 CCl3 〉 CHCl2 〉 CH2Cl ∼ CH3. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI3)3- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ∼ 14.5 mol %) by 13C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)2 and Co(acac)3-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.
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  • 107
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2193-2201 
    ISSN: 0887-624X
    Keywords: ring-opening polymerization ; poly(trimethylene carbonate) ; butyltin tri-chloride ; cationic mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerous BuSnCl-3, Bu2SnCl-2, and Bu3SnCl-initiated polymerizations of cyclo(tri-methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initiators, but their reactivities decrease in the order BuSnCl3 〉 Bu2SnCl2 〉 Bu3SnCl. The maximum molecular weights decrease in the same order. With BuSnCl3 Mws up to 250,000 were obtained. These molecular weights were determined by GPC on the basis of the universal calibration method. In this connection Mark-Houwink equations for two solvents, tetrahydrofuran (THF) and CH2Cl2 were determined and compared with literature data. Furthermore, mechanistic aspects were studied. 1H- and 13C- NMR spectra revealed that BuSnCl3 forms complexes with the CO-group of TMC, whereas Bu2SnCl3 do not cause NMR spectroscopic effects. Kinetic studies in chloroform and nitrobenzene and a comparison with Bu3SnOMe suggest that at least BuSnCl3 initiates a cationic mechanism. However, in contrast to SnCl4 (or SnBr4), BuSnCl3 does not cause decarboxylation. Regardless of the initiator 1H-NMR spectroscopy revealed CH2OH and CH2CI endgroups in all cases. © 1995 John Wiley & Sons, Inc.
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  • 108
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2241-2250 
    ISSN: 0887-624X
    Keywords: poly(amide-imide)s ; trimellitic acid ; smectic-A phase ; phase transition ; synchrotron radiation ; bâttonet texture ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycondensation of α, ω-bis(-4-aminophenoxy) alkanes with trimellitic anhydride chloride (TMA-Cl) in m-cresol yielded a new class of poly(amideimide)s. Starting from the same diamine spacers poly(amideimides) with a more regular sequence of amide and imide groups were prepared by another synthetic method. All these poly(amide-imide)s are semi-crystalline and melt in the range of 250-300°C. They form a smectic-A phase over a narrow temperature range and suffer thermal degradation at the isotropization temperature (330-350°C). The smectic-A phase was characterized by optical microscopy (“batonnet texture”) and by synchrotron radiation measurements conducted at a heating rate of 20°C. Furthermore, it is demonstrated that slight variation of the chemical structure, such as methyl substituents or meta positions in the spacer prevent the formation of a LC phase. © 1995 John Wiley & Sons, Inc.
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  • 109
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 621-627 
    ISSN: 0887-624X
    Keywords: phenolic-triazine ; cyanate ester ; phenol formaldehyde resin ; cardanol ; cyclotrimerization ; matrix resin ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cardanol incorporated-phenol-formaldehyde novolac resins were synthesized by acid and base catalyzed reactions. The novolacs were transformed to their cyanate esters. The thermal cure characteristics of the cyanate esters depended upon the composition. The presence of cardanol proportionately facilitated the curing. The thermal characterization of the novolacs and the corresponding cured phenolic-triazine networks indicated a dedicated a detremental effect of cardanol on the thermal stability and char residue of the resins. © 1995 John Wiley & Sons, Inc.
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  • 110
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 633-642 
    ISSN: 0887-624X
    Keywords: free radicals ; grafting ; kinetics ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22-0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130-160°C temperature range was, however, surprisingly low, 42±5 kJ mol-1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc.
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  • 111
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 653-663 
    ISSN: 0887-624X
    Keywords: photopolymerization ; poly(indanes) ; cationic polymerization ; photopolymerizable poly(imide)s ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of monomers containing isopropenylphenoxy groups was carried out. On irradiation with UV light in the presence of onium salt photoacid generators, these monomers undergo a chain extension reaction consisting of a dimerization followed by a Friedel-Crafts ring closure which results in the formation of polymers with indane groups in the backbone. Aryl imide-containing monomers bearing isopropenylphenoxy groups were also shown to undergo facile photoinduced cationic polymerization. The resulting polymers displayed excellent thermal stability. © 1995 John Wiley & Sons, Inc.
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  • 112
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2339-2345 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The state of p-phenylphenol molecules in dioxane/water mixture, a commonly used reaction system for enzymatic polymerization of phenols and aromatic amines, was investigated by difference UV absorption spectroscopy and Fourier transform (FT) Raman spectroscopy. The aggregate of p-phenylphenols is found on the basis of the exciton peaks observed in difference UV absorption spectra. FT Raman spectroscopy demonstrates further that p-phenylphenol molecules aggregate together in “face to face” fashion. A simplified model is proposed for aggregation of p-phenylphenol molecules in dioxane/water mixture, which can elucidate the variation of the molecular weight of poly (p-phenylphenol) coupled in the reaction system. © 1995 John Wiley & Sons, Inc.
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  • 113
    ISSN: 0887-624X
    Keywords: soluble ethynylene-containing polyamides ; palladium-catalyzed polyconden-sation ; ethynylene-bearing amide monomers ; thermal behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New ethynylene-containing aromatic polymides were synthesized by the carbon-carbon crosscoupling polycondensation of aromatic diiodides with aromatic amide-bearing diethynyl compounds in the presence of a palladium catalyst, cuprous iodide, and an organic base. The polymers having sulfone linkages were soluble in various organic solvents and their weight average molecular weights were in the range of 12,500 and 26,500. The polymers with the highest inherent viscosity were obtained, when the monomer ratio of a diethynyl compound to a diiodide was 1.01. The polymers showed no detectable glass transition temperature and no weight loss up to around 300° C in nitrogen. The thermal crosslinking of the polymers occurred at 280°C through the existing internal ethynylene group. © 1995 John Wiley & Sons, Inc.
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  • 114
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2393-2402 
    ISSN: 0887-624X
    Keywords: metallocene, supported ; polypropylene, isotatic ; propylene polymerization, kinetics of, modelling of ; polyolefins, particle growth model for ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several propylene polymerizations are carried out with supported metallocene catalyst, prepared by reaction of silica gel with methylaluminoxane and then with rac-dimethylsi-lanediylbis(indenyl)zirconiumdichloride. The rate-time curves obtained are analyzed to understand the influence of support and triisobutylaluminium on the reaction. As a first attempt to model this system we developed a partially new praticle growth model, based on a shell by shell fragmentation hypothesis (gradual break-up from the outside to the inside of the particle), and a final multigrain structure of the particle. A kinetic scheme including the TIBA interaction with the supported catalyst is also presented. The model prediction and the experimental data are compared for the rate-time curves and polymer properties. © 1995 John Wiley & Sons, Inc.
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  • 115
    ISSN: 0887-624X
    Keywords: 3-fluoro-4′-(11-vinyloxyalkoxy)-4-biphenyl (2R,3S)-2-fluoro-3-methylpen-tanoate ; “living” cationic polymerization ; liquid crystallinity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and “living” cationic polymerization of 3-fluoro-4′-(11-vinyloxyundecany-loxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate (12-11) and 3-fluoro-4′-(8-vi-nyloxyoctyloxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate (12-8) are presented. Poly (12-11)s and poly (12-8)s with degrees of polymerization from 4.0 to 16.5 and poly-dispersities ≤ 1.13 have been synthesized and characterized by differential scanning cal-orimetry (DSC) and thermal optical polarized microscopy. Over the entire range of molecular weights poly (12-11)s and poly (12-8)s exhibit an enantiotropic SA and an unidentified SX phase. In addition, regardless of its molecular weight, poly (12-8) exhibits a S*c phase in between the SA and Sx phases. Poly (12-11) and poly (12-8) show lower transition tem-peratures and broader temperature ranges of all their mesophases as compared to the corresponding polymers without a fluorine atom on the biphenyl group. The role of the connecting group between the biphenyl and chiral group of the mesogenic unit on the phase behavior of these polymers is also discussed. Copolymers of 12-8 with (2R,3S)-2-fluoro-3-methylpentyl 4′-(11-vinyloxyundecanyloxy)biphenyl-4-carboxylate (13-11) {i.e., poly-[(12-8)-co-(13-11)] (X/Y), where X/Y represents the molar ratio of monomer 12-8 to monomer 13-11} with DP of ca. 11 and polydispersities lower than 1.23 were also syn-thesized and characterized. Their SA and S*c mesophases exhibit continuous dependences of composition and this support the assignment of the mesophases exhibited by poly (12-8). © 1995 John Wiley & Sons, Inc.
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  • 116
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2415-2423 
    ISSN: 0887-624X
    Keywords: photoinitiated cationic polymerization ; 1-propenyl ethers ; siloxanes ; 1-pro-penyl ether-functionalized siloxanes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 1-propenyl ether-functionalized siloxanes (PFS) has been achieved by the controlled, rhodium-catalyzed, chemoselective hydrosilation of 1-allyloxy-4(1-propen-oxy) butane with various H-functional siloxanes. It was shown that the hydrosilation pro-ceeds exclusively at the allyl ether group of 1-allyloxy-4(1-propenoxy) butane without par-ticipation at the 1-propenyl ether group. The photoinduced cationic polymerization of these monomers was studied using various analytical techniques and found to take place very rapidly. © 1995 John Wiley & Sons, Inc.
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  • 117
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2443-2447 
    ISSN: 0887-624X
    Keywords: polyaniline ; oxalic acid dopant ; EPR ; IR ; UV/V ; TGA ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaniline-oxalic acid salts were prepared at 5 and 30°C by chemical polymerization of aniline using different concentration of oxalic acid. Polyaniline base was obtained from the corresponding polyaniline salt by dedoping using aqueous ammonium hydroxide solution. Conductivity measurements, elemental analysis, Infrared, electronic absorption, electron paramagnetic resonance spectral, and thermogravimetric analysis were performed on the polyaniline salts and bases. Composition and the extent of dopant in polyaniline salt systems where determined. The value of composition of polyaniline: oxalic acid is 4: 1.6 and the polymer yield is around 66%. The value of conductivity, polymer yield and composition of polyaniline-oxalic acid salt is independent of concentration of oxalic acid used and also the synthesis temperature. The results are compared with polyaniline-hydrochloride salt prepared by chemical polymerization. The conductivity of polyaniline-oxalic acid salt is three orders of magnitude lower than that of polyaniline-hydrocholoride salt. © 1995 John Wiley & Sons, Inc.
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  • 118
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2435-2441 
    ISSN: 0887-624X
    Keywords: poly(o-phenylenediamine) ; solubility ; conducting polymer ; molecular structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A conducting polymer, poly(o-phenylenediamine) (PoPD), has been obtained as stable film onto an electrode surface by the electropolymerization of o-phenylenediamine in 0.1 mol dm-3 H2SO4. The film thickness did not exceed 0.85 μm because of its low electrical con-ductivity. The virgin “doped” polymer film was soluble in dimethylsulfoxide N, N-dimeth-ylformamide, acetone, and tetrahydrofuran without any pretreatment. The highest solubility obtained was 17 g dm-3 in dimethylsufoxide. A cast film of PoPD on a substrate was prepared from its dimethylsulfoxide solution. The mean molecular weight of PoPD was found to be 11,000 with the gel permeation chromatography. The STM observation exhibited that the cast film was considerably uniform compared to the electrodeposited film. The cyclic voltammogram of such film showed a reversible redox property accompanied with excellent electrochromism between transparent yellow and brown. It was suggested from the 1H-FTNMR and FTIR spectra and the elemental analysis that the polymeric backbone has 1, 4-substituted benezenoid-quinoid structure. © 1995 John Wiley & Sons, Inc.
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  • 119
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2463-2471 
    ISSN: 0887-624X
    Keywords: cycloaliphatic epoxides ; mechanistic studies ; photoinitiated cationic poly-merization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a series of difunctional epoxides bearing two epoxycyclohexyl groups linked together by an alkylene ether group has been carried out. Subsequently, the reactivities of these novel monomers was investigated and compared to the reactivity of the cycloali-phatic epoxide, 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexane carboxylate (I) in pho-toinitiated cationic polymerization. It was observed that alkylene oxide linking the two epoxycyclohexyl groups was short and the monomers are more reactive than I. The effects of the photoinitiator structure and the experimental conditions of the cationic photopo-lymerization on the rates was also studied using real-time infrared spectroscopy. © 1995 John Wiley & Sons, Inc.
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  • 120
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2515-2519 
    ISSN: 0887-624X
    Keywords: thymine styrene monomer ; functional styrene monomer ; multifunctional monomer ; photoresist ; photocrosslinking ; photopolymer ; 2π + 2π photocyclization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 121
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2505-2513 
    ISSN: 0887-624X
    Keywords: neodymium ; polybutadiene ; alkylaluminum ; alkylaluminum chloride ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ternary neodymium-based catalyst for the polymerization of 1,3-butadiene, Nd(versatate)3/Ali-Bu2H/tert-butyl chloride, has been examined with respect to the effects of a range of alkylaluminums and alkylaluminum chlorides. Using either pre-formed or in situ catalysts, observations pertaining to catalyst activity and physical state and the characteristics of the final polymer are discussed. The catalyst activity series with the type of alkylaluminum was found to be: Aln-Pr3 ≫ Aln-Dodec3 = Aln-Oct3 = Aln-Hex3 〉 Ali-Bu2H 〉 Ali-Bu3 〉 AlEt3 ≫ AIMe3. Polybutadiene cis content was found to vary with the type of alkylaluminum used. Pre-formed catalysts using methylaluminum chlorides as chloride source were found to be the most active; AlMe2Cl chloride gave the highest activity. The activity of in situ catalysts prepared using alkylaluminum chlorides was found to be independent of alkylaluminum chloride structure. Polybutadiene prepared using catalysts based on different alkylaluminums and alkylaluminum chlorides was found to decrease in cis content with conversion. © 1995 John Wiley & Sons, Inc.
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  • 122
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2521-2522 
    ISSN: 0887-624X
    Keywords: gelatin ; sol-gel transition ; metal ions ; viscosity ; radiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 123
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2533-2549 
    ISSN: 0887-624X
    Keywords: free radical ; grafting ; kinetics ; model ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft site initiation occurs by primary radical and/ or polymeric radical attack on the back-bone polymer. The controlling mechanism is determined by the structure of the backbone and the activity of the free radicals. The efficiency of incorporating monomer into the graft chains depends upon the graft site initiation mechanism and the mode of polymer chain termination (recombination or disproportionation). A kinetic analysis results a series of uniquely different expressions describing the graft efficiency, φ corresponding to different combinations of graft site initiation and chain termination mechanisms. The dependency of φ upon monomer, initiator, and backbone concentrations is different from case to case. The complete kinetic model is capable of predicting reaction rate, graft efficiency, graft frequency, graft ratio, and molecular weight averages and distributions. Simulations are provided to compare predicted results with experimental data for two different systems which show contrasting mechanisms of graft site initiation and mode of termination. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2613-2621 
    ISSN: 0887-624X
    Keywords: solution conformation ; amphoteric copolymer ; 14N-NMR ; 23 Na-NMR ; poly-electrolyte ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solution conformations and dynamic mobilities of novel amphoteric copolymers were studied for aqueous solutions of p(sodium 2-methacryloxyethanesulfonate-co-2-methacryloy-loxyethyltrimethylammonium iodide) [P(NaMES-co-METMAI)] as a function of com-position, concentration, and addition of HCI or KCI. As HCI or KCI was added successively to 5 w/v% copolymer solutions, the reduced viscosities of the solutions were reduced except the 1:1 copolymer solution. The dynamic mobility of the cationic side chain was estimated with the quadrupolar 14N-NMR relaxation technique. The motion of the interacting coun-terion, Na+, was studied by Poisson-Boltzmann electrostatic theories and the quadrupolar 23Na-NMR. Since the intramolecular 1:1 ion pair between MES- and METMA+ acts as an effective charge-screening factor, the copolymers P(NaMES-co-METMAI) behave as ordinary polyelectrolytes with the exception of the 1 : 1 copolymer. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2605-2612 
    ISSN: 0887-624X
    Keywords: complex formation ; PEO ; copolymer ; phenolic resin ; hydrogen bonding ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Comb copolymers formed from acrylamide and poly(ethylene-glycol) methacrylate macro-monomer (PAM-co-PEG) were compared to poly(ethylene oxide) (PEO) with respect to hydrogen bond complex formation with water-borne phenolic resins. The behaviors of the two types of high molecular weight polyethers were similar. Complex formation gave a transient increase in viscosity followed by precipitation. Copolymers with pendant PEG chain lengths ≥ 9 formed complexes with phenolic resin whereas PEG homopolymer with a molecular weight of 2000 did not form a complex. For both copolymer and high molecular weight PEO, the tendency of the complex to precipitate increased when the pH was decreased from 7 to 4. Acridine orange, a cationic dye, bound to the phenolic resin and, after the addition of PEO, yielded visible complex gels with diameters about 20 μm. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2657-2665 
    ISSN: 0887-624X
    Keywords: amphiphilic rubber ; butyl rubber ; saccharide ; microphase-separated structure ; thermoplastic elastomer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new type of amphiphilic elastomer was synthesized, which consisted of butyl rubber and a D-maltose derivative as a backbone and side groups, respectively. The synthesis was accomplished by the sequence of the three following reactions: (1) Hydroxyl groups of D-maltonolactone were protected by a trimethylsilyl group. (2) The resulting maltonolactone derivative was subjected to a reaction with chemically modified butyl rubber having pendant amino groups. (3) The protecting trimethylsilyl groups on the maltose residues were removed by treating with tetra-n-butylammonium fluoride. This new amphiphilic elastomer behaved as a thermoplastic elastomer and showed good mechanical properties. The saccharide seg-ments aggregated in the hydrophobic butyl rubber matrix to form a microphase-separated structure, as confirmed by differential scanning calorimetry, transmission electron mi-croscopy, small-angle x-ray scattering, and dynamic mechanical measurements. The ag-gregated saccharide domains are estimated to function both as crosslinking sites and rein-forcing fillers in the rubber matrix. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2673-2680 
    ISSN: 0887-624X
    Keywords: main chain LCPs ; ionic LCPs ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An ionogenic main chain liquid crystalline polymer was synthesized. In contrast to previous studies the charged sites were incorporated into the flexible spacer and not into the mesogenic group. This was done through quaternization of 1,2-bis(4-pyridylethane) with a biphenyl-4,4′-nonanoxytoluenesulphonate. The polymer displayed thermotropic and lyotropic me-sophases. The thermotropic mesophase was smectic. Organic counterions such as meth-ylsulfonates and p-toluenesulfonates were found to be favorable to the development of mesophases, due to the increased solubility and lower isotropisation temperatures, when compared to bromide counterion containing polymers. Easy supercooling, dependence on thermal history, and the development of batonnet textures on cooling from the melt were also observed. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2705-2714 
    ISSN: 0887-624X
    Keywords: coumarin derivatives ; photodimerization ; photocleavage ; reversible ; pho-tosensitizer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four photoreactive coumarin derivatives were successfully synthesized from 7-hydroxy-coumarin and 7-hydroxy-4-methylcoumarin, i.e., 7-propionyloxy-4-methylcoumarin (M1), 7-palmitoyloxy-4-methylcoumarin (M2), 7-propionyloxycoumarin (M3), and 7-palmitoy-loxycoumarin (M4). Reversible photodimerization (350 or 300 nm) and photocleavage (254 nm) of these coumarin derivatives dispersed in poly(vinyl acetate) (PVAc) were investigated by tracing their UV absorbance variations at 310 nm. The M2 and M4 with long palmitoyl chain show much better photoreaction reversibility than M1 and M3 with short propionyl chain. Moreover, photodimerization rate (under 350 nm) of M2 is greater than 200 times of that of M1. This has been explained by the formation of suitable conformation for revers-ible photodimerization due to the hydrophobic interactions. Photodimerization of M2 is ca. 3 times quicker than that of M4, indicating 4-methyl substitution enhances pho-todimerization. The influence of photodimerization wavelength (350 and 300 nm) and photosensitizer (benzophenone) have also been investigated in detail. © 1995 John Wiley & Sons. Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2741-2752 
    ISSN: 0887-624X
    Keywords: 3,3′-bis (4-flurobenzoyl) biphenyl ; poly (aryl ether ketone)s ; spectroscopic prop-erties ; thermal properties ; thermomechancial properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A monomer, 3,3′-bis (4-fluorobenzoyl) biphenyl, was prepared in high yield in two steps from inexpensive 3-chlorobenzoyl chloride and fluorobenzene, and polymerized by nucleophilic displacement reaction with various bisphenol monomers in tetramethylene sulfone to produce a series of high molecular weight poly(aryl ether ketone)s containing 3,3′-dibenzoylbiphenyl (DBBP) moieties. The spectroscopic, thermal, and thermomechanical properties of these polymers and related isomeric polymers having 2,2′-and 4,4′-DBBP units were determined and compared to study the effects of changes in the substitution pattern of the biphenyl unit. Except for the 2,2′-DBBP series of polymers, Tgs were found to increase with increasing linearity of the DBBP unit. The 2,2′-DBBP series of polymers had exceptionally high Tgs due to the sterically restricted motions in the biphenyl unit caused by the 2,2′-substitution. In addition, they also showed evidence for torsion with the 2,2′-DBBP unit, whereas in other isomeric polymers the DBBP units are believed to be relatively coplanar. Thermal stabilities and tensile moduli for these polymers proved to be independent of substitution patterns. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2787-2793 
    ISSN: 0887-624X
    Keywords: Ziegler-Natta catalysis ; EPDM synthesis ; metallocene catalyst ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Vinylcyclohexene (VCH) and cyclooctadiene (COD) were investigated as termonomers in EPDM (ethylene/propylene/diene) synthesis by using rac-ethylenebis (1-η5-indenyl) zir-conium dichloride (1) as a catalyst precursor. Homopolymerizations of VCH, vinylcycloh-exane and cyclohexene were compared. The parameter Kπκp, which is the apparent rate constant for Ziegler-Natta polymerization, is about the same for VCH and vinylcyclohexanebut is 10 times smaller for cyclohexene. Therefore, the linear olefinic double bond is more active than the cyclic internal double bond. VCH reduces ethylene polymerization rate but not propylene polymerization rate in copolymerizations. In terpolymerizations, VCH tends to suppress ethylene incorporation especially at elevated polymerization temperature and Lowers the polymer MW by about two-fold. COD has very low activity as a termonomer. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2865-2873 
    ISSN: 0887-624X
    Keywords: fumarate ; radical polymerization ; addition-abstraction mechanism ; ESR spectrum ; propagation rate constant ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radical polymerization behavior of ethyl ortho-formyl-phenyl fumarate (EFPF) using dimethyl 2,2′-azobisisobutyrate (MAIB) as initiator was studied in benzene kinetically and ESR spectroscopically. The polymerization rate (Rp) at 60°C was given by Rp = k[MAIB]0.76[EFPF]0.56. The number-average molecular weight of poly(EFPF) was in the range of 1600-2900. EFPF was also easily photopolymerized at room temperature without any photosensitizer probably because of the photosensitivity of the formyl group of monomer. Analysis of 1H- and 13C-NMR spectra of the resulting polymer revealed that the radical polymerization of EFPF proceeds in a complicated manner involving vinyl addition and intramolecular hydrogen-abstraction. The polymerization system was found to involve ESR-observable poly(EFPF) radicals under the actual polymerization conditions. ESR-determined rate constant (2.4-4.0 L/mol s) of propagation at 60°C increased with decreasing monomer concentration, which is mainly responsible for the observed low de-pendency of Rp on the EFPF concentration. Copolymerizations of EFPF with some vinyl monomers were also examined. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2841-2850 
    ISSN: 0887-624X
    Keywords: aromatic copolyesters ; poly(ethylene terephthalate) ; poly(ethylene naphtha-late) ; melt polycondensation ; physical properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolyesters containing rigid segments (naphthalene and terephthalene) and flexible seg-ments (aliphatic diol) structure were synthesized from DMN/DMT/EG (2,6-dimethyl naphthalate/1,4-dimethyl terephthalate/ethylene glycol) ternary monomers with various mole ratios. Copolyesters having intrinsic viscosities of 0.52-0.65 dL/g were obtained by melt polycondensation in the presence of metallic catalysts. The effect of reaction tem-perature and time on the formation of the copolyesters was investigated to obtain an op-timum condition for copolyester manufacturing. The optimum condition for PNT (poly-ethylene naphthalate terephthalate) copolyester manufacturing is the transesterification under nitrogen atmosphere for 4 h at a temperature of 185±2°C followed by polymerization under 2 mm Hg for 2 h at a temperature of 280°C. Most copolyesters have better solubilities than poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) in various solvents. The effect of the starting mole ratio of DMN, DMT, and EG on the thermal properties of the resulted copolyesters was also investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of copolyesters were in the range of 70.7-115.2°C, and 10% weight loss in nitrogen were all above 426°C. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2893-2899 
    ISSN: 0887-624X
    Keywords: poly(p-phenylenebenzobisthiazole) ; poly(p-phenylenebenzobisoxazole) ; fiber ; molecular composite fiber ; benzocyclobutene ; compressive strength ; tensile strength ; tensile modulus ; phase separation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fibers consisting of a rigid rod polymer and thermoset resin matrices were prepared. Poly(benzo-[1,2-d : 5,4-d′]bisoxazole-2,6-diyl)-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with isophthaloyl bis-4-benzocyclobutene (1) or 2,6-bis-4-benzocyclobutene benzo[1,2-d: 5,4-d′]bisoxazole (2), and fibers were spun from these dopes. As-spun fibers that did not show phase segregation between the two components as examined with an optical microscope, were soluble in methanesulfonic acid (MSA). After heat treat-ment, the fibers swelled but did not dissolve in MSA. A fiber cross section of heat-treated PBO-1 fiber showed well-dispersed benzocyclobutene polymer domains of 200-500 Å by transmission electron microscopy (TEM). Films cast from MSA solutions of PBO and 2 were homogeneous, and TEM of heat-treated fiber showed only one phase. A molecular composite fiber was made. Some of these fibers showed 20-30% improvement in compressive strength over unmodified PBO fiber. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2887-2892 
    ISSN: 0887-624X
    Keywords: plasma ; cascade arc ; surface modification ; fluorination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The depth and possible mechanisms of the penetration of surface modification into porous media by a low temperature cascade are torch are investigated. Two different modes of such penetration (“flow controlled” and “diffusion controlled”) are evaluated. Three porous samples [stacks of 10 sheets of nonwoven fabrics of poly(ethylene terephthalate)each], placed at an axial distance of 24, 28, and 32 cm from the cascade are anode, are exposed to a low temperature cascade arc torch containing argon and CF4 or C2F4, and surface properties of each of the sheets within treated porous samples are examined by ESCA. It is shown that interaction of chemically reactive species, created in the low temperature cascade arc torch, with the surface is not limited to the surface directly contacted by the torch. The flow controlled penetration is more pronounced for the outer layers, while diffusion controlled penetration is within the inner layers of the porous structure. Substantial differences in the fluorination effect of CF4 (nonpolymer forming gas) and C2F4 (polymer forming gas) discharges for the second and third stacks are observed, that can be explained by the fact that the major effect of the CF4 cascade arc torch treatment is based on the reaction of reactive species with the surface polymer molecules. The effect of C2F4 cascade arc torch treatment is based on the reactions of reactive species with polymers as well as reactions of reactive species themselves at the surface (plasma polymerization). Reactivity of the species created in C2F4 discharge is much higher compared to that created in CF4 discharge, which is one of the major factors influencing penetration trends of low temperature cascade arc treatment into porous media. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 333-339 
    ISSN: 0887-624X
    Keywords: reactivity ratios ; microstructure ; 13C-NMR spectroscopy ; (vinyl acetate)/(glycidyl methacrylate) copolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Vinyl acetate)/(glycidyl methacrylate) (V/G) copolymers were prepared by free radical solution polymerization in benzene. Copolymer composition was determined by 1H-NMR spectroscopy. Comonomer reactivity ratios were calculated by Kelen-Tüdos (KT) and error-in-variables (EVM) methods. The values reactivity ratios calculated by these methods are rV = 0.03 ± 0.01; rG = 38.9 ± 6.20 (KT) and rV = 0.03 ± 0.002; rG = 39.5 ± 1.97 (EVM). The microstructure of V/G copolymers in terms of the distribution of V and G centered was obtained from 13C{1H}-NMR spectra using the carbonyl carbon resonance signals of V as well as G units. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 873-877 
    ISSN: 0887-624X
    Keywords: 4,4′-diamino-3′-nitrobenzanilide (DNB) ; poly-p-benzamide (PBA) ; poly-p-benzamide end-capped with nitro-p-phenylenediamine ; polyterephthalamide of 4,4′-diamino-3′-nitrobenzanilide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 891-900 
    ISSN: 0887-624X
    Keywords: mercury-dithizone ; photochromic probes ; thermal relaxation rate ; free volume ; Tg ; thermal transition ; polystyrene ; poly(vinyl acetate) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mercury-dithizone complex both free and bonded to a polymeric system has been synthesized and used to measure the thermal transition of polystyrene, poly(vinyl acetate), and some other polymers. The thermal relaxation rate of the activated complex in dark has been found to be dependent on the free volume of a polymer matrix. The rate goes through a maximum above Tg of a polymer. A very sensitive method, based on thermal recovery of activated photochromic probe chromophore has been devised to measure the thermal transition of both single and multicomponent polymer matrices. © 1995 John Wiley & Sons, Inc.
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    ISSN: 0887-624X
    Keywords: poly(ethylene oxide) ; (poly(oxy-1,2-ethanediyl) ; PEO ; hydrogen peroxide ; hydroxyl radicals ; hydroperoxyl radicals ; chain scission process ; oxidative degradation ; photodegradation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene oxide) (poly(oxy-1,2-ethanediyl) is rapidly oxidized by hydroxyl (HO•) and hydroperoxyl (HO•2) radicals generated by photolysis of hydrogen peroxide (H2O2) or by the catalytic decomposition of H2O2 by metallic silver. This process is accompanied by a chain scission during which the molecular weight decreases and the polydispersity changes. As a result of this process, the crystalline structure of poly(ethylene oxide) disappears, and the polymer becomes completely amorphous. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 117-124 
    ISSN: 0887-624X
    Keywords: polyimide ; polyamide ; adamantane ; thermal properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Diaminoadamantane (I) was used as a monomer with various aromatic dicarboxylic acyl chlorides and dianhydrides to synthesize polyamides and polyimides, respectively. Polyamides having inherent viscosities of 0.10-0.27 dL/g were prepared by low-temperature solution polycondensation. The polyamides were soluble in a variety of solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), pyridine, dioxane, and nitrobenzene. These polyamides had glass transition temperatures in the 179-187°C range and 5% weight loss temperatures occurred at up to 354°C. Polyimides based on diamine I and various aromatic dianhydrides were synthesized by the two-stage procedure that included ring-opening to form polyamic acids, followed by thermal conversion to polyimides. The polyamic acids had inherent viscosities of 0.14-0.38 dL/g. The glass transition temperature of these polyimides were in the 245-303°C range and showed almost no weight loss up to 350°C under air and nitrogen atmosphere. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 141-148 
    ISSN: 0887-624X
    Keywords: polyacrylic acid ; silicone rubber membrane ; plasma-induced graft polymerization ; homobifunctional membrane ; 1,1-diphenyl-2-picryhydrazyl ; surface modification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyacrylic acid (PAA) was grafted onto the surface of silicone rubber membrane (SR) by plasma-induced graft copolymerization (PIP). Ar-plasma was used to activate the surface of SR. Also, a determination was made of the influences of plasma treatment power, pressure, time, grafted copolymerization reaction time, and monomer concentration on polymerization yield. The surface properties of SR were measured by ATR-FTIR, ESCA, and SIMS. In those analyses, the elemental composition and different carbon bindings on the surface of SR were examined by ESCA with the amount of O1s/C1s being approximately 0.7 at 60 s by Ar-plasma treatment (60 W, 200 mtorr). The peroxide group introduced on SR was measured via 1,1-diphenyl-2-picryhydrazyl (DPPH). The optimum amount of peroxide groups was 6.85 × 10-8 mol/cm2 at 60 s of Ar-plasma treatment. The peroxide group (33D peak) was introduced onto the surface of SR by negative spectra of SIMS analysis after SR treatment by Ar-plasma. An increase was obtained in grafted polymerization yield with a region of 5 to 50% (v/v) of acrylic acid aqueous solution. Both sites of polyacrylic acid were detected after staining by toluidine blue O. That is, a homobifunctional membrane was developed via this surface modification method. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 261-270 
    ISSN: 0887-624X
    Keywords: chemically modified polymers ; addition reactions ; carboxybetaines ; reaction mechanisms and kinetics ; pyridines ; imidazoles ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed study of the synthesis of betaine products that result from addition reactions of poly (4-vinylpyridine) and poly (N-vinylimidazole) as well as of their model compounds, with α,β-unsaturated monocarboxylic acids is presented. A reaction mechanism based on experimental observations and proved by kinetic analysis is proposed. It consists of two reactions: the addition, which involves two molecules of acid and leads to X+B--like structures, where the cation X+ results from the addition of the amino nitrogen to the double bond of acid and B- is the carboxyl anion, and an equilibrium reaction between X+B- and the betaine structure X±. The latter occurs only in protic solvents and is coupled with the addition reaction. The process was especially investigated in methanol, because this solvent allows determination of the kinetic parameters. Some values of the addition rate constants are given. The study is based on 1H-NMR measurements and observations. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 301-303 
    ISSN: 0887-624X
    Keywords: thermosensitive polymer ; water soluble polymer ; polymer modification reaction ; poly(vinylamine) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 157-163 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From data in the literature on relative rates of copolymerization it has been possible to evaluate two constants, Q and e, characteristic of an individual monomer, which appear to account satisfactorily for its behavior in copolymerization. The constant Q describes the “general monomer reactivity” and is apparently related to possibilities for stabilization in a radical adduct. The constant e takes account of polar factors influencing copolymerization.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 357-365 
    ISSN: 0887-624X
    Keywords: processable polyimides ; poly(pyromellitimide)s ; rigid-rod polyimides ; polyimides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From imidazole-blocked 2,5-bis[(n-alkyloxy)methyl]-1,4-benzene diisocyanates and pyromellitic dianhydride a series of new rigid-rod polyimides (Cn-PY-PI; n = 4, 6, 8) having linear and flexible (alkyloxy)methyl ((SINGLE BOND)CH2OCnH2n + 1; n = 4, 6, 8) side chains were prepared and characterized and their properties were measured and discussed with regard to effects of side chains. Incorporation of the side chains onto the rigid main chain greatly enhanced the solubility and fusibility of the polymers, and melting point of C8-PY-PI was determined to be 277°C. The UV-VIS absorption behavior was independent of side-chain length. TGA thermograms revealed a two-step pyrolysis behavior, in which the side chains split off separately at lower temperatures. X-ray diffractograms showed that all the polyimides are crystalline at room temperature. Sharp reflections in small-angle region obviously indicated the presence of a layered crystal structure. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 481-492 
    ISSN: 0887-624X
    Keywords: poly(benzobisthiazoles) ; sulfonated poly(benzobisthiazoles) ; rigid rod polymers ; polyelectrolytes ; thermally stable polymers ; conducting polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polyelectrolytes based on sulfonated poly(benzobisthiazoles) (PBTs) have been synthesized by a polycondensation reaction of sulfo-containing aromatic dicarboxylic acids with 2,5-diamino-1,4-benzenedithiol dihydrochloride (DABDT) in freshly prepared polyphosphoric acid (PPA). Several sulfonated PBTs, poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-2-sulfo-1,4-phenylene] sodium salt (p-sulfo PBT), poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-5-sulfo-1,3-phenylene] sodium salt (m-sulfo PBT), their copolymers, and poly[(benzo[1,2-d:4,5-d′]bisthiazole-2,6-diyl)-4,6-disulfo-1,3-phenylene] potassium salt (m-disulfo PBT), have been targeted and the polymers obtained characterized by 13C-NMR, FT-IR, elemental analysis, thermal analysis, and solution viscosity measurements. Structural analyses confirm the structures of p-sulfo PBT and m-disulfo PBT, but suggest that the sulfonate is cleaved from the chain during synthesis of m-sulfo PBT. m-Disulfo PBT dissolves in water as well as strong acids, while p-sulfo PBT dissolves well in strong acids, certain solvent mixtures containing strong acids, and hot DMSO. TGA indicates that these sulfonated PBTs are thermally stable to over 500°C. Free-standing films of p-sulfo PBT, cast from dilute neutral DMSO solutions, are transparent, tough, and orange in color. Films cast from basic DMSO are also free standing, while being opaque and yellow-green. p-Sulfo PBT was incorporated as the dopant ion in polypyrrole, producing conductive films with conductivities as high as 3 S/cm and electrical anisotropies as high as 10. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 979-987 
    ISSN: 0887-624X
    Keywords: Ziegler-Natta polymerization ; EPDM ; metallocene catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethylene (E), propylene (P), and 1,4-hexadiene (HD) were terpolymerized with rac-1,2-ethylenebis (1-η5-indenyl) zirconium(IV) dichloride and methylaluminoxane (Et[Ind]2ZrCl2/MAO), and compared with the copolymerizations of E/P, E/HD, P/HD, and terpolymerization using ethylidene norbornene (ENB) as the termonomer. HD lowers the polymerization activity, the effect is more pronounced for P/HD and E/P/HD using large amount of P, than for E/HD and E/P/HD using feed low in P. The polymer molecular weight is most strongly affected by the temperature of polymerization (Tp), whereas the E/P ratio in the feed has virtually no effect. The reactivity ratios rE and rP are 3.0 and 0.3, respectively, at 20°C but rP becomes larger than rE at TP = 70°C. 1H-NMR spectra showed occurrence of cycloaddition in the homopolymerization of HD; on the other hand, HD is incorporated in the terpolymer only by linear 1,2-addition. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 517-518 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 721-728 
    ISSN: 0887-624X
    Keywords: polyurethane ; metal ions ; synthesis ; coordination ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyurethane organometallic complexes based on novel diols, bis[N-[[2-hydroxyphenyl]methylene]hydroxylethyleneamino]-copper(II) (DBSICu), were synthesized successfully. The products are elastomeric glassy materials or powders. Similar to other polyurethane elastomers, these coordination block copolymers exhibit 2-phase microstructure and thermoplastic properties. It is interesting to note that some of these polyurethanes show a Schlieren pattern under the polarizing optical microscope. The liquid crystalline properties of DBSICu and the coordination polymers are studied in detail in this study. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 747-754 
    ISSN: 0887-624X
    Keywords: poly(amide-imide)s ; bis(trimellitimide)s ; 3,3-bis[4-(4-aminophenoxy)phenyl]-phthalimidine ; triphenyl phosphite John Wiley & Sons, Inc. ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of novel bis(phenoxy)phthalimidine-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 3,3-bis[4-(4-aminophenoxy)phenyl]phthalimidine (BAPP) with various aromatic bis(trimellitimide)s in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III, having inherent viscosities up to 1.36 dL/g, were obtained in quantitative yields. All resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 267-322°C and the 10% weight loss temperatures were above 490°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III′ prepared from 3,3-[4-(4-trimellitimidophenoxy)phenyl]-phthalimidine and various aromatic diamines. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 801-809 
    ISSN: 0887-624X
    Keywords: zwitterion ; hydroxide inner salt ; polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zwitterion, 1-[4-[(4-hydroxy-1-naphthyl)thio]butyl]quinuclidinium hydroxide inner salt, was synthesized from tetrahydro-1-(4-hydroxy-1-naphthyl)thiophenium hydrochloride and quinuclidine and characterized by NMR and IR spectroscopy. Polymerization of the zwitterion was studied over the temperature range 175-225°C. The polymer was identified as poly(1,4-piperidinediylethyleneoxy-1,4-naphthylenethiotetramethylene) based on NMR and IR spectroscopy. The polymer was found to contain 3-butenylthio and 4-hydroxy-1-naphthyl end groups. Based on the signal area of the olefinic end group, the polymer M⊼n varied between 8500 and 13,000. The highest molecular weight was achieved at the lowest temperature, indicating that termination became more favored at higher temperature. A mechanism is proposed to describe the polymerization. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 833-838 
    ISSN: 0887-624X
    Keywords: allyl glycidyl ether ; acrylonitrile ; copolymerization ; gamma-rays ; reactivity ratios ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of allyl glycidyl ether (AGE) with acrylonitrile (AN) have been prepared by bulk polymerization of their monomers with gamma rays. Copolymers thus obtained were characterized by Fourier transform infrared (FTIR), and ultraviolet (UV) spectroscopic techniques. The composition of the copolymers is determined indirectly by FTIR, UV, and directly by elemental analysis. The results obtained by different methods are compared. The reactivity ratios of monomer pairs (AGE + AN) which copolymerized heterogeneously were calculated by using different methods of determination. Among the three experimental methods used for the analysis of compositions and two theoretical methods of computations, the elemental analysis technique and the application of nonlinear least-squares method gave the most reliable reactivity ratios. These are found to be 1.86 and 0.21 for acrylonitrile and allyl glycidyl ether, respectively. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 869-884 
    ISSN: 0887-624X
    Keywords: hot-melt polycondensation ; siloxane-modified sulfone-containing epoxy resin ; PMPS ; PDMS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Siloxane-modified sulfone-containing epoxy resins (ESBS) were prepared by polycondensation of PMPS and/or PDMS siloxane oligomers with EBS, the sulfone-containing epoxy resin. Structures were analyzed by IR, 1H-, and 13C-NMR. The siloxane content in the copolymers was determined by 1H-NMR with an integration technique. Epoxy equivalent weight (EEW) determination indicated that the oxirane ring of EBS was intact with this hot-melt procedure. The GPC measurement of these ESBS copolymers showed that molecular weight (MW) increased with increasing siloxane content in PMPS-modified copolymers. Evidence of siloxane incorporation in the copolymer was discussed. © 1996 John Wiley & Sons, Inc.
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  • 153
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    Keywords: chain transfer ; addition-fragmentation ; peroxysilane ; radical polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoate 1, ethyl 2-[1-(dimethylvinylsilylperoxy)-ethyl]propenoate 2, ethyl 2-[1-(1-(2-ethoxycarbonyl-1-methyl-2-propenylperoxysilyl)-1-methylethylperoxy)ethyl]propenoate 3, and 2-phenyl-2-trimethylsilylperoxypropane 4 were synthesized and added to the free radical polymerization of vinylic monomers. 1 and 2 were found to show no homopolymerizability but act as effective chain transfer reagents in radical polymerizations of methyl methacrylate (MMA), styrene (St), and n-butyl acrylate (BA). The estimated chain transfer constants (Ctr) are as follows: Ctr (1) = 0.15 for MMA, 0.90 for St, and 2.03 for BA at 60°C; Ctr (2) = 0.12 for MMA, 1.16 for St, and 1.9 for BA at 60°C. 1H-NMR spectra of poly(St) formed in the presence of 1 is consistent with the view that the polymers bear an oxirane at one terminal and an trimethylsilyloxy fragment at the other end. Moreover, peroxysilane 4 showed very low transfer properties by direct homolytic substitution (SH2). These findings indicate that the ethyl 2-[1-(substituted dimethylsilylperoxy)ethyl]-propenoates 1-3 undergo chain transfer reaction via a intramolecular homolytic substitution (SHi) following an addition process. Preparation of poly(styrene) up to high conversion in the presence of 3 yielded to the formation of the corresponding polymeric structures bearing hydrolysable C(SINGLE BOND)O(SINGLE BOND)Si(SINGLE BOND)O(SINGLE BOND)C bonds. © 1996 John Wiley & Sons, Inc.
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  • 154
    ISSN: 0887-624X
    Keywords: emulsion terpolymerization ; control of microstructure ; monomer addition profile ; chemical composition distribution ; gradient polmer elution chromatography ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An optimal addition profile for the preparation of a chemically homogeneous emulsion terpolymer of styrene, methyl methacrylate, and methyl acrylate was determined using a recently developed model for describing composition drift in emulsion co- and terpolymerizations. TRISEPS, described in Part I of this series. The model uses recently published simplified equations to describe monomer partitioning and the terminal model for describing terpolymer composition. The optimal addition rate profile was determined from the calculated optimal addition profile with a purely empirical and iterative method. With gradient polymer elution chromatography (GPEC®) the homogeneity and/or heterogeneity of the terpolymers prepared in the iterative series of experiments could be determined and compared to the heterogeneity of the corresponding batch terpolymer described in Part I. It was shown that a homogeneous terpolymer could be obtained indicating that the simplified equations for monomer partitioning and the terminal model for terpolymer composition describe the system adequately. It was also shown that GPEC® was useful in the determination of the optimal addition rate profile. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 985-990 
    ISSN: 0887-624X
    Keywords: monovinylacetylene ; poly(vinylacetylene) ; anionic polymerization ; titration ; tertiary butyllithium ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A polymer consisting of a saturated carbon backbone with pendent acetylenic groups was prepared from monovinylacetylene. A titration was performed between the monomer and tertiary butyllithium, its lithiating agent. The charge transfer complex formed between the solvent THF and the tertiary butyllithium was used as an indicator of the unreacted butyllithium. Hence, a stoichiometric quantity of tertiary butyllithium was added dropwise to a solution of monovinylacetylene in THF to form lithiovinylacetylene. The addition of a slight excess of butyllithium led to the polymerization of the lithiated monomer. The obtained polymer was reprotonated and characterized. This polymerization was evaluated as a possible route to synthesize poly(vinylacetylene) with processable molecular weights, for its application as a potential carbon fiber precursor. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 971-984 
    ISSN: 0887-624X
    Keywords: radiation ; polyisobutylene ; NMR ; GC/MS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: GC, GC/MS, GPC, and Solution NMR spectra were used to study the γ radiolysis of polyisobutylene (PIB) in vacuum to different total doses (0-900 kGy) and at different temperatures (77-423 K). NMR spectra show a large number of new resonances with relatively narrow line widths, and a variety of NMR techniques have been employed to determine and quantify the structures associated with these new resonances. Chemical shift assignments were made by comparison with those for small molecule model compounds and predictions based upon calculations according to several different schemes. Chain-end structures have been proposed that account well for the majority of the new resonances, all being the result of an initial chain scission reaction initiated by the radiation. These assignments support some previous proposals for the mechanism of radiation degradation of polyisobutylene and exclude others. For example, NMR provides no evidence for the formation of ethyl chain ends and some of the main chain unsaturated structures previously proposed. NMR also indicate that at higher doses the chain end products formed during initial stages undergo secondary reactions. GC/MS data show the formation of oligomers during irradiation, which may be due to a backbitting mechanism. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1015-1024 
    ISSN: 0887-624X
    Keywords: ambifunctional monomers ; 1-propenyl ethers ; 1-butenyl ethers ; vinyl ethers ; cationic polymerization ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a novel series of ambifunctional monomers containing cationically polymerizable vinyl and 1-propenyl ether or 1-butenyl ether groups in the same molecule has been carried out. Studies of the onium salt-induced photopolymerizations of these monomers indicate that both functional groups are highly reactive and that they undergo extensive copolymerization. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1083-1085 
    ISSN: 0887-624X
    Keywords: poly(metyhylene sulfide) ; condensation polymerization ; catalysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation polymerization of sodium sulfide with methylene chloride in various solvents was studied in order to assess the influence of polarity on the yield and composition of condensation products. The effect of addition of polyethylene glycol was also studied. It has been found that the overall yield of polythiomethylenes rises from 13.9% in methanol to 85.2% (methanol, PEG15000). The use of solvents of higher polarity promotes the linear oligomers, whereas in methanol the cyclic products predominate. In presence of PEG the this equilibrium is shifted towards tetrathiane. The observed phenomena are discussed in terms of solvents polarity and reaction media viscosity. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 909-910 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1183-1188 
    ISSN: 0887-624X
    Keywords: anionic polymerization ; polybutadiene ; triallylstannyllithium ; star polymer ; reversible chain transfer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anionic polymerization of 1,3-butadiene using a novel metalloidal anion initiator, triallylstannyllithium (TALi)-allyllithium (ALi), was studied. The TALi-ALi initiated anionic polymerization of 1,3-butadiene gave the star polymer along with the linear polybutadiene (PBD). The star polymer consisted of three PBD branches and a central tin atom. What is striking is a fact that the number-average molecular weights (Mn) and molecular weight distribution of three PBD branches and linear PBD were almost identical. A reversible chain transfer polymerization mechanism, which includes the equilibrium between tri(macroallyl)-stannyllithium and macroallylic anion, is proposed. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1203-1208 
    ISSN: 0887-624X
    Keywords: plasma polymerization ; graft polymerization ; polyethylene ; poly(methylacrylate) ; membrane ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a plasma-induced graft polymerization technique, which is well known as a surface modification method, the grafted polymer was formed in pores of the porous material. This study examined the filling mechanism. Five thin porous films were sandwiched together, and employed as the substrate. The substrate was treated by plasma, and the change in surface tension and radical formation was measured for each sheet after the sheet was separated. The only surface on which surface-tension change was detected, was that of the sheet directly exposed to the plasma. Although plasma treatment made polymer radicals primarily on the outer surface of the sheet, the treatment also formed a few radicals inside the sheets. The radicals inside the sheets reacted with methylacrylate and grafted polymer formed in the pores. The location of grafted polymer depended on the balance between monomer diffusivity and reactivity. The grafting rate depended on which monomer solvent was used for the polymerization. Thus, the grafted membrane morphology could be controlled by varying the grating solvent composition. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1095-1105 
    ISSN: 0887-624X
    Keywords: 1,6-bis(4-aminophenoxy)naphthalene ; direct polycondensation ; polyamides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new bis(phenoxy)naphthalene-containing diamine, 1,6-bis(4-aminophenoxy)naphthalene, was synthesized in two steps from the condensation of 1,6-dihydroxynaphthalene with p-chloronitrobenzene in the presence of potassium carbonate, giving 1,6-bis(4-nitrophenoxv)naphthalene, followed by hydrazine hydrate/Pd - C reduction. A series of polyamides were synthesized by the direct polycondensation of the diamine with various aromatic dicarboxylic acids in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved metal salts such as CaCl2 or LiBr using triphenyl phosphite and pyridine as condensing agents. The polymers were obtained in quantitative yield with inherent viscosities of 0.78-3.72 dL/g. Most of the polymers were soluble in aprotic solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), NMP, and they could be solution-cast into transparent, flexible and tough films. The casting films had tensile strength of 102-175 MPa, elongation at break of 8-42%, and tensile modulus of 2.4-3.8 GPa. The polymers derived from rigid dicarboxylic acids such as terephthalic acid and 4,4′-biphenyldicarboxylic acid exhibited some crystalline characteristics. The glass transition temperatures of the polyamides were in the range of 238-337°C, and their 10% weight loss temperatures were above 487°C in nitrogen and above 438°C in air. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1119-1124 
    ISSN: 0887-624X
    Keywords: poly(vinyl alcohol) ; silylation ; hexamethyldisilazane ; liquid ammonia ; kinetics ; properties ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silylation of poly(vinyl alcohol) has been performed with hexamethyldisilazane in liquid ammonia in an autoclave. This novel procedure has the advantage that the educt, the reagent, and the product are soluble in ammonia, which works under homogeneous conditions. No salt like by-products are formed and no tedious purification of the product is necessary. The degree of silylation has been adjusted through the ratio of silylating agent to hydroxy groups. Random incorporation of trimethylsilyl groups was proven by the linear dependence of the glass transition temperature from the degree of silylation and the solubility of the partially silylated material. Quantitative investigation of the silylation reaction showed first-order kinetics for the initial and final stages of the reaction indicative of a reaction where k1 〉 k2 〉 k3. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1107-1118 
    ISSN: 0887-624X
    Keywords: polystyrene ; glycidyl methacrylate ; methyl methacrylate ; epoxy ; emulsion polymerization ; seeded growth ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Colloidal polystyrene particles with surface epoxy groups have been synthesized through surfactant-free emulsion copolymerization of styrene with glycidyl methacrylate; and through copolymerization of glycidyl methacrylate (GMA) and methyl methacrylate as shells around existing polystyrene seed particles. We developed two titration methods to quantify the number of epoxy groups that survived the polymerization processes. The styrene-GMA copolymer particles were judged to be unsatisfactory as model colloidal materials due to their size polydispersity and unknown internal distribution of epoxy groups. The core-shell particles had high epoxy surface densities with at least 60% of the initial epoxy groups surviving the synthesis process. Transmission electron microscopy shows that the thickness of the epoxy-rich shell is less than expected based on the volume of monomers added, suggesting that some of the monomer forms water-soluble oligomers. Photon correlation spectroscopy measurements imply that the shell is swollen with water and consists of polymer configurations which extend out into solution. The morphological details vary consistently with the GMA content, and hence the hydrophilicity, of the shell polymer. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1133-1142 
    ISSN: 0887-624X
    Keywords: Diels-Alder polyaddition ; coronand structure ; bispyrones ; bismaleimides ; polyimides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of various substituted bis(2-pyrone)s with bismaleimides in dilute solution was carried out to produce linear soluble polymers with coronand structure. The number-average molecular weights of the polymers ranged from 7000 to 18,000 (vapor pressure osmometry). Polymer structures were identified by NMR spectroscopy and model reactions. The stereochemistry and the mechanism are discussed. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1125-1132 
    ISSN: 0887-624X
    Keywords: butadiene ; polymerization ; neodymium ; molecular weight ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homopolymerization of 1,3-butadiene in a stirred batch reactor with the catalytic system Nd octoate/diethyl-aluminium chloride/triisobutyl-aluminium in n-heptane was studied. The effect of various reaction conditions on especially high conversion and molecular weight is reported. Polymerization is shown to be first order with respect to both monomer and neodymium. Molecular weights are high and broadly distributed. Chain transfer to triisobutylaluminium is the main factor governing molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1143-1151 
    ISSN: 0887-624X
    Keywords: poly(aryl ether ketone)s ; amorphous ; thermally stable ; fluorinated polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two novel fluorinated monomers were prepared and polymerized with biphenols to produce amorphous, thermally stable poly(aryl ether ketone)s. The properties of the fluorinated polymers are compared to those of unfluorinated, amorphous poly(aryl ether ketone)s. The presence of fluorine in the polymers was found to cause a decrease in glass transition temperature and Young's moduli, however, no increase in thermal stability was observed. The fluorinated polymers are soluble in common organic solvents such as chloroform and methylene chloride at room temperature, and also show solubility in solvents containing a ketonic moiety, such as acetone. Evidence of polymer branching through fluorines considered to be unreactive under the polymerization conditions was found. Efforts were made to evaluate the reactivity of fluorine atoms under the polymerization conditions using both molecular modeling and 19F-NMR to ascertain if such branching could be avoided. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1433-1441 
    ISSN: 0887-624X
    Keywords: aromatic polyamides ; ether-dicarboxylic acids ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,4′-(1,4-Phenylenedioxy)dibenzoic acid (3), 4,4′-(2,5-tolylenedioxy)dibenzoic acid (Me-3), and 4,4′-(2,5-biphenylenedioxy)dibenzoic acid (Ph-3) were prepared by the nucleophilic substitution reaction of p-fluorobenzonitrile with hydroquinone, methylhydroquinone, and phenylhydroquinone, respectively, followed by alkaline hydrolysis. Several aromatic polyamides having inherent viscosities of 0.66-1.34 dL/g were directly prepared by a Yamazaki phosphorylation polyamidation technique from dicarboxylic acids 3, Me-3, and Ph-3, respectively, with aromatic diamines using triphenyl phosphite and pyridine as condensing agents. The solubility of methyl- or phenyl-substituted polyamides was remarkably enhanced when compared to that of nonsubstituted analogues. Most of the substituted polyamides revealed an amorphous nature and were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, dimethyl sulfoxide, and m-cresol. Transparent, flexible, and tough films of these polymers could be cast from the DMAc or NMP solutions. These films had tensile strength of 60-100 MPa, elongation to break of 6-11%, and tensile modulus of 1.68-2.25 GPa. The glass transition temperatures (Tg) of most polyamides could be determined by differential scanning calorimetry (DSC) and were in the range of 200-232°C. Thermogravimetric analyses established that these polymers were fairly stable up to 450°C, and the 10% weight loss temperatures were recorded in the range of 458-535°C in nitrogen and 468-528°C in air atmosphere. In general, the phenyl-substituted polyamides exhibited relatively higher Tg, thermal stability, and solubility. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1475-1482 
    ISSN: 0887-624X
    Keywords: anion exchange membranes ; electrodialysis ; relative transport number between two anions ; effect of hydrophobicity on anion transport ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A membranous copolymer crosslinked with divinylbenzene reacted with N,N,N′,N′-tetra-methylethylenediamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, and N,N,N′,N′-tetramethyl-1,6-hexanediamine to prepare highly crosslinked anion exchange membranes. More than 80% of both tertiary amino groups of the diamines reacted with chloromethyl groups of the membrane to form crosslinkage. After formation of the high crosslinkage of the membrane was confirmed with dialysis of a neutral molecule, electrochemical properties of the obtained membranes (mainly, relative transport number between two anions in electrodialysis) were evaluated: nitrate ions to chloride ions, sulfate ions to chloride ions, fluoride ions to chloride ions, and bromide ions to chloride ions. Though larger anions, in general, were difficult to permeate through the membranes due to high crosslinkage, the number of methylene groups of the diamines (which means the increase in hydrophobicity of anion exchange groups) also affected the relative transport number between two anions. The lower the hydration of anions, the higher the relative transport number of the anions through the membranes with the hydrophobic anion exchange groups. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1493-1500 
    ISSN: 0887-624X
    Keywords: 2,7-bis(4-maleimidophenoxy)naphthalene ; bismaleimide ; Michael addition ; naphthalene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinking of 2,7-bis(4-maleimidophenoxy)naphthalene (BMPN) and 4,4-bismaleimi-dophenylmethane (BMPM) was investigated in the presence of 4,4-diaminodiphenylmethane (DDM) at the 2/1 molar ratio of bismaleimide/DDM. Their curing behaviors were characterized by infrared spectroscopy and differential scanning calorimetry. The presence of a naphthalene group in the backbone of the bismaleimide increased the curing temperature and reduced the polymerization reactivity. The exotherm was shifted to a lower temperature as the amine addition lead to chain extension. Thermal behavior and properties of cured products were investigated by thermogravimetric analyses and dynamic mechanical analyses. Also, at this molar ratio, the properties of the BMPN/DDM showed better Tg, thermal decomposition temperature, and moisture resistance than the epoxy derived from 2,7-dihydroxynapthalene cured with DDM system (DGEDN/DDM). © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1517-1527 
    ISSN: 0887-624X
    Keywords: anionic polymerization ; styrenic monomers ; aggregate reactivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The long-standing presumption that aggregated organolithium species are unreactive in hydrocarbons has been examined for styryllithium head-groups. A computer based curve-fitting evaluation of the equilibrium constants assumed to govern the perceived dimer: singlet equilibria for polystyryllithium in benzene, cyclohexane, and toluene was done. From the calculated concentrations of singlet head-groups and the experimental propagation rates, the rate constant (kp) values were obtained. Some values were approximately equal to or larger than those measured for the ion-pair in etherial solvents. These hydrocarbon solution values are improbably large, raising serious doubts about the validity of the mechanism upon which they are based. The data for the styrenic monomers in toluene also failed to lend support to that mechanism. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1581-1588 
    ISSN: 0887-624X
    Keywords: aromatic polyesters ; soluble aromatic polyesters ; alkoxy or phenyl substituted aromatic polyesters ; rigid polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rigid aromatic polyesters containing alkoxy or phenyl-substituted oligophenyls were prepared. Soluble polymers were obtained also in cases where phenyl-substituted quinquephenyl diols were combined with asymmetric phenyl-substituted terephthalic acid. The synthesized polyesters were characterized by viscosimetry, gel permeation chromatography, thermal analysis, and dynamic mechanical analysis. The temperature dependence of the intrinsic viscosity was sensitive to the type of side groups. Thermogravimetry has shown that polyesters with aromatic substituents were stable up to 380-400°C. The glass transition temperatures of the polyesters with aromatic side groups were in the 220-260°C range as determined by DSC. Polyesters with hexyloxy side chains show crystallinity. Dynamic mechanical analysis showed that in the cases where aromatic substituents were used to increase solubility, the obtained polymers have very useful mechanical properties at high temperatures. The polymer having the quinquephenyl unit in the main chain has an almost constant modulus up to 340°C. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1343-1346 
    ISSN: 0887-624X
    Keywords: citral ; reactivity ratios ; error-in-variables ; substituted styrenes ; methyl methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1347-1351 
    ISSN: 0887-624X
    Keywords: biopolymer ; alkaline hydrolysis ; molecular weight control ; microorganism ; poly(γ-glutamic acid) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1483-1491 
    ISSN: 0887-624X
    Keywords: epoxidation ; epoxide ; functionalization ; partial hydrogenation ; styrene ; butadiene ; block copolymer ; SBS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of partially saturated lightly functionalized styrene-butadiene block copolymers of polyA-block-polyB-block-polyA type (SBS) is described. The work involves epoxidizing partially hydrogenated SBS block copolymers using peracetic acid in a cyclohexane/water heterogeneous system. Five partially hydrogenated model polymers containing low levels of unsaturated aliphatic double bonds were used to study the epoxidation reaction and kinetics. The existence of the epoxide functional group on the product polymer was evidenced by IR and 1H-NMR spectra and the epoxide concentration was determined by direct titration. The partially hydrogenated SBS copolymers were more difficult to epoxidize than the unhydrogenated ones. The temperature dependence of the epoxidation rate was studied and the activation energy was determined as 8.8 kcal/mole of double bonds. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1407-1414 
    ISSN: 0887-624X
    Keywords: molecular orbital method ; MOPAC ; transition state ; addition polymerization ; ethylene ; methyl acrylate ; methyl methacrylate ; dimethyl itaconate ; N-methyl itaconimide ; differential photocalorimetry ; DPC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (Eas) show good correlations with experimental values. Calculated activation entropies (-ΔS
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1529-1541 
    ISSN: 0887-624X
    Keywords: living cationic polymerization ; methyl tri(ethylene glycol) vinyl ether ; isobutyl vinyl ether ; diblock copolymers ; water-soluble polymers ; amphiphiles ; micelles ; hydrodynamic size ; critical micelle concentration ; cloud point ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble diblock copolymers of methyl tri(ethylene glycol) vinyl ether (hydrophilic block) and isobutyl vinyl ether (hydrophobic block) of different molecular weights and composition were synthesized by living cationic polymerization. The molecular weight and comonomer composition of these copolymers were determined by GPC and 1H NMR spectroscopy, respectively. Aqueous solutions of the copolymers were characterized in terms of their micellar behavior using dynamic light scattering, aqueous GPC, and dye solubilization. All the copolymers formed aggregates with the exception of a diblock copolymer with only two hydrophobic monomer units. The micellar hydrodynamic size scaled with the 0.61 power of the number of hydrophobic units, in good agreement with a theoretical exponent of 0.73. An increase in the length of the hydrophobic block at constant hydrophilic block length or an increase in the overall polymer size at constant block length ratio both resulted in lower critical micelle concentrations (cmcs). The cloud points of 1% w/w aqueous solutions of the polymers were determined by turbidimetry. An increase in the length of the hydrophobic block at constant hydrophilic block length caused a decrease in the cloud points of the copolymers. However, an increase in the overall polymer size at constant block length ratio led to an increase in the cloud point. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1421-1431 
    ISSN: 0887-624X
    Keywords: polyamides ; “five-ring” ; dicarboxylic acids ; fluoro-displacement ; triphenyl phosphite ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The five benzene rings-containing (hereafter referred to as “five-ring”) dicarboxylic acids α,α′-bis[4-(4-carboxyphenoxy)phenyl]-1,4-diisopropylbenzene (p-III) and α,α′-bis[4-(4-carboxyphenoxy)phenyl]-1,3-diisopropylbenzene (m-III) were prepared by the fluoro-displacement of α,α′-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene and α,α′-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene with p-fluorobenzonitrile, and subsequent alkaline hydrolysis of the intermediate dinitriles. A number of high-molecular-weight polyamides based on these two “five-ring” dicarboxylic acids (p-III and m-III) and various aromatic diamines were directly synthesized in N-methyl-2-pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl2) using triphenyl phosphite and pyridine as condensing agents. These polyamides were obtained with inherent viscosities above 0.51 and up to 0.91 dL/g. The weight-average molecular weight were in the range of 51,000-211,000. Most of these polyamides were amorphous and readily soluble in polar solvents such as NMP, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and afforded tough, flexible, and transparent films by solution-casting. The films had tensile strength of 50-83 MPa, elongation to break of 4-8%, and tensile modulus of 1.3-2.0 GPa. Most polyamides showed distinct glass transitions on the differential scanning calorimetry (DSC) curves ranging from 147 to 177°C. In nitrogen or air, all the polymers showed no significant weight loss up to 490°C, as indicated by thermogravimetric analysis (TG). © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1511-1516 
    ISSN: 0887-624X
    Keywords: poly(ethylene terephthalate) ; surface treatment ; VUV photochemistry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) was exposed to radiation from different kinds of low-pressure plasmas in an oxygen atmosphere. The lower wavelength limit of the spectrum investigated, λ = 112 nm, is the cut-off of magnesium fluoride used for separating the specimen chamber from the plasma light source. The total surface oxygen concentration, and the formation of hydroxyl, carbonyl, and carboxyl groups were evaluated from XPS measurements in combination with chemical derivatizations, and their dependences on the radiation spectrum and the oxygen pressure in the sample chamber have been investigated. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1543-1552 
    ISSN: 0887-624X
    Keywords: polyester ; polyolefin and blend ; macromonomer and epoxy ; epoxy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods for preparing saturated polyolefin oligomers with Si(SINGLE BOND)H, epoxy groups, and with dihydroxy groups have been developed. Anionic polymerization of butadiene, then termination of the chains with chlorodimethylsilane leads to controlled molecular weight oligomers with silane functionality, and wherein the microstructure can be tailored. Hydrogenation of these materials proceeds smoothly using colloidal nickel catalysts to yield the corresponding saturated materials, which are stable to conditions used for melt polyesterifications. Hydrosilation of allyl glycidyl ether with the Si(SINGLE BOND)H end groups produces epoxy functional oligomers, and subsequent hydrolysis of the epoxy rings yields oligomers with a dihydroxy group at one end. Melt copolymerization of the olefin macromers with 1,4-butanediol and 1,4-dimethylcyclohexanedicarboxylate in the presence of titanium isopropoxide affords poly(ester-g-olefin) graft copolymers. These copolymers are under study as model interfacial agents for polyester/polyolefin blends and as suspension agents for polyester particles in nonpolar media. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1553-1560 
    ISSN: 0887-624X
    Keywords: conducting polymers ; poly(isothianaphthene) ; mechanism of formation ; phthalic anhydride ; phthalide ; phosphorus pentasulfide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results of some mechanistic studies on the formation of poly(isothianaphthene) from phthalic anhydride and phthalide by reaction with phosphorus pentasulfide (P4S10) are described. Based on the observed intermediates during the polymerization and their reactivity, it is proposed that both reactions occur by a sequence of substitution (thionation), isomerization, and polymerization reactions. P4S10 is the most efficient reagent for the conversion of phthalic anhydride and phthalide, and Lawesson's Reagent (a commonly used thionating reagent) gives less satisfactory results. It is suggested that P4S10 assists the rate-determining step. Oxygen-containing monomers do not polymerize in the absence of a thionating reagent under the conditions for the synthesis of PITN, thereby keeping the incorporation of oxygen into the polymeric backbone to a minimum. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1567-1572 
    ISSN: 0887-624X
    Keywords: pyrolysis ; polypyrrolone film ; electrical conductivity ; carbonization ; graphitization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of the pyrolytic temperature on the structure of the pyrolyzed polypyrrolone (PMDA-DAB) films were investigated. The structure of pyrolyzed PMDA-DAB film was characterized by elemental analysis, XPS spectra, x-ray diffraction, and SEM images. It suggests that the pyrolysis process of PMDA-DAB films consists of carbonization and graphitization processes, and the transitional temperature is at ca. 800°C. During carbonization process (Tp 〈 800°C), most oxygen is removed and the enhancement of conductivity with the pyrolytic temperature may be due to an extended conjugation of π-electron orbitals resulting in an increase of the number of charge carriers. During graphitization (Tp 〉 800°C), both oxygen and hydrogen are removed completely, and an increase in the mobility of charge carriers may increase conductivity with pyrolytic temperature. A graphite-like structure with heterocyclic rings containing nitrogen atoms is proposed for the PMDA-DAB film pyrolyzed at 1200°C. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1609-1611 
    ISSN: 0887-624X
    Keywords: copper(I) iodide ; p-xylylene dibromide ; potassium carbonate ; poly[(p-xylylene carbonate)-co-(p-xylylene oxide)] ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1589-1595 
    ISSN: 0887-624X
    Keywords: graft polymerization ; peroxide group ; carbon black ; polymeric peroxide ; radical trapping ; vinyl polymer ; dispersibility ; e-value ; surface modification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The introduction of peroxide groups onto carbon black surface was achieved through the trapping of the peroxide radicals formed by the decomposition of polymeric peroxide, such as poly(tetraethylene glycol peroxyadipate) (ATPPO), and bis-peroxide, such as 1,1′-bis (t-butyldioxy)cyclohexane (Perhexa-C), by the surface: the amount of peroxide groups introduced onto carbon black surface by the treatment with ATPPO and Perhexa-C were determined to be 0.07 mmol/g and 0.12 mmol/g, respectively. The polymerization of vinyl monomers with positive e-value, such as methyl methacrylate and 2-hydroxyethy methacrylate, was successfully initiated by the peroxide groups introduced onto carbon black surface. During the polymerization, the corresponding polymers were effectively grafted onto the surface as a result of the propagation of polymer from the surface radicals formed by decomposition of the peroxide groups. The polymerization of vinyl monomers with negative e-value, such as styrene and vinyl acetate, however, was scarcely initiated by the peroxide groups on carbon black. This may be due to the fact that surface active radicals, which were formed by the hydrogen abstraction from carbon black by fragment radicals, inhibit the polymerization of vinyl monomers with negative e-value. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1613-1615 
    ISSN: 0887-624X
    Keywords: ethyl nitrate ; DMSO ; poly(vinyl ester) ; poly(vinyl acetal) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1617-1621 
    ISSN: 0887-624X
    Keywords: dipropargyl derivatives ; carbazole ; palladium-catalyzed polycondensation ; crosslinking ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1373-1383 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Many 2,6-disubstituted phenols are readily oxidized with oxygen, a tertiary amine and a copper (I) salt being used as catalyst. The products are diphenoquinones (I) or 1,4-polyphenylene ethers (II):The effect of variation of the substituents on the phenol and the infrared spectra of the polymers is discussed. Amine complexes of copper salts are the only effective catalysts found for the polymer-forming reaction. The effect on the catalyst of varying the copper salt and the ligand is discussed.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1651-1655 
    ISSN: 0887-624X
    Keywords: polybutenes ; ethene-propene copolymer ; amidoalkylation ; trifluoroacetic acid ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amidoalkylations of polybutenes and of ethene-propene copolymer, catalyzed by trifluoroacetic acid, result in 5,6-dihydro-4H,1,3-oxazino-substituted polyalkenes with the 2-position of the oxazine ring unsubstituted or occupied by a vinyl or a phenyl group. The vinyl-substituted dihydrooxazino polymers thus obtained readily add butylamine to the vinyl fragment yielding alkylamino-substituted derivatives. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1819-1822 
    ISSN: 0887-624X
    Keywords: cyclic carbonate ; L-phenylalanine ; ο-hydroxy carboxylic acid ; polycondensation ; DCC ; DMAP ; poly(ester-urethane) ; 1-methyl-2-fluoropyridinium salt ; trypsin ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1823-1826 
    ISSN: 0887-624X
    Keywords: hybrid inorganic/organic IPN ; porous materials ; poly(styrene) ; silica gel nanotubes ; mesoporous hexagonal silica ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1713-1721 
    ISSN: 0887-624X
    Keywords: polyurethane anionomers ; ionic diols ; methylene spacers ; TGA ; DSC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionic diols with varying methylene spacers were prepared from maleic anhydride and linear diols. Reaction across the unsaturated site by aqueous sodium bisulphite was used to prepare the ionic diols. Chain extended polyurethane ionomers were prepared by the reaction of prepolymer based on different polyols and diisocyanates with the ionic diols. The polyurethane anionomers were characterized by FT-IR and FT-NMR spectroscopy. The differential scanning calorimetric results show that Tg of the anionomers shifted towards low values as the ionic content in the polyurethane increases and as the length of the ionic diol increases. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1733-1740 
    ISSN: 0887-624X
    Keywords: LC side-group block copolymer ; morphology ; phase separation ; LC behavior ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid crystalline triblock copolymers with LC inner block and amorphous outer blocks have been synthesized by “living” anionic polymerization and investigated using DSC, TEM, and small-angle x-ray diffraction. All samples of poly[styrene-block-2-(3-cholesteryloxycarbonyloxy) ethyl methacrylate-block-styrene] (PS-b-PChEMA-b-PS) show liquid crystalline behavior and phase separation between the blocks. Compared to triblock copolymers with PS inner block (PChEMA-b-PS-b-PChEMA) and diblock copolymers (PS-b-PChEMA) the LC block copolymers with PS outer blocks have the same properties. The LC behavior and the morphology do not depend on the block arrangement; they are only influenced by the volume fractions of the blocks. Those samples in which the liquid crystalline subphase is not continuous (spheres) only a nematic phase was found, whereas in all samples with a continuous liquid crystalline subphase, the smectic A phase of the homopolymer was observed. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1753-1761 
    ISSN: 0887-624X
    Keywords: photopolymerization ; copolymers ; hydrogels ; biocompatible polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The study of the homo- and copolymerization of furfuryl methacrylate (F) and vinylpyrrolidone (P) in bulk, initiated by the photoactivation of AIBN at low temperatures (0 and 40°C), is described. The kinetic diagrams for the homopolymerization of F and P were obtained following the evolution of the heat of reaction by DSC, and revealed the autoacceleration and the vitrification effects on the polymerization rate. The influence of oxygen in the photoinitiated polymerization was analyzed by determining the steady-state concentration of oxygen from the kinetic data obtained for polymerizations performed out in the presence and absence of oxygen. The results obtained indicate that P is more sensitive than F to the presence of oxygen in free radical polymerization. The photoinitiated copolymerization process is little affected by the concentration of monomers, giving similar Rp and θm values for both systems. However, at low polymerization temperature 0°C non-crosslinked copolymers are obtained, whereas at a temperature of 40°C, the copolymers prepared at conversion higher than 20 mol % become crosslinked as a result of the active participation of the furfuryl ring in the polymerization process at this temperature. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1783-1792 
    ISSN: 0887-624X
    Keywords: bis[4-(2-hydroxyethoxy)aryl] compound ; copolyester with naphthalene groups ; melt polycondensation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolyesters containing naphthalene structure were synthesized from bis(hydroxyethyl)naphthalate (BHEN) or bis(hydroxybutyl)naphthalate (BHBN) and various aralkyloxy diols. The starting bis[4-(2-hydroxyethoxy)aryl] compounds were derived from a nucleophilic substitution of various bisphenols with ethylene carbonate in the presence of KI. Copolyesters having intrinsic viscosities of 0.45-0.60 dL/g were obtained by the melt polycondensation in the presence of metallic catalysts. The effect of reaction temperature and time on the formation of copolyesters were investigated to obtain an optimum condition for copolyesters manufacturing. Most copolyesters have better solubilities than polyethylene naphthalate (PEN) or polybutylene naphthalate (PBN) in aprotic solvents, such as N-methyl-2-pyrrolidone or m-cresol. The thermal properties of the copolyesters were investigated by the differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures (Tg) of copolyesters result from BHEN were in the range of 90-141°C, and 10% weight loss in nitrogen were all above 460°C. Another series of copolyesters result from BHBN have Tg in the range of 75-135°C, and 10% weight loss in nitrogen of over 420°C. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1815-1818 
    ISSN: 0887-624X
    Keywords: 1,3-pentadiene ; cationic polymerization ; crosslinking ; chain transfer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1629-1629 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1827-1828 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1633-1634 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1635-1649 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When, in a poly-α-olefin, the probability that a given placement be isotactic depends upon the tacticity of only a finite number of immediate predecessors, the resulting diastereosequence distribution obeys the theory of Markoff chains. When this is not the case, one says that the resulting diastereosequence distribution is non-Markoffian. A special case of a Markoffian distribution is given by a simple Markof chain in which the tacticity of a given placement is assumed to be affected by only the tacticity of the immediately preceding placement. Another special case is, of course, the Bernoulli trial distribution in which the probability that a given placement be isotactic is independent of the tacticity of all other placements. A high resolution NMR spectrum can sometimes yield a quantitative determination of the concentrations of isotactic and syndiotactic placements and the concentrations of the three types of possible adjacent pairs of such placements (i.e., isotactic, syndiotactic, and heterotactic pairs). When this is the case, the spectrum can be used to determine whether or not a given diastereosequence distribution is Bernoullian. However, because the longest diastereosequences whose concentration can be measured by NMR spectroscopy involve only two placements, an NMR spectrum cannot check whether a given non-Bernoullian distribution be simple Markoffian or Markoffian in general. In fact, non-Markoffian distributions are compatible with existing NMR spectra on polymers prepared by anionic polymerizations. In this paper we work within the framework of Kac's theory of stationary statistical processes and point out some general results which are valid for both Markoffian and non-Markoffian processes. The results are applied to NMR spectroscopy and it is pointed out which calculations used to check the self-consistency of NMR data and to obtain the mean length of closed diastereosequences are valid for both Markoffian and non-Markoffian distributions.
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    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1873-1880 
    ISSN: 0887-624X
    Keywords: cation exchange membranes ; pre-irradiation grafting ; FEP ; styrene ; states of water ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure and some physico-chemical properties of radiation grafted FEP-g-polystyrenesulfonic acid proton exchange membranes were studied as a function of the degree of grafting. The distribution of grafted polymer across the membrane thickness was obtained from microprobe measurements. It was found that for low levels of grafting (ca. 3%), polystyrene chains are located near the membrane surface only, and the interior of the membrane remains ungrafted. With the increasing degree of grafting, polystyrene chains were incorporated into the interior of the membrane as well. An almost homogeneous distribution of grafts in the membrane was obtained at a graft level of 〉 13%. The influence of the degree of grafting on membrane properties, such as ion exchange capacity, swelling, and specific resistivity was studied. Three different states of water, viz., freezing free, freezing bound, and nonfreezing water have been identified in noncrosslinked membranes. However, the nature and the amount of crosslinker had a profound influence on the states of water in a membrane. © 1996 John Wiley & Sons, Inc.
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