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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The network formation of phenol-formaldehyde resin was investigated by the Monte Carlo (MC) simulation technique. The observed value of the gel point, pc, was exactly determined as a critical extent of reaction, where the Mw/Mn in soluble parts is maximum. The MC simulation with the cubic percolation theory was applied to the gelation of phenolic resins and gave an exact gel point, which was in excellent agreement with the observed value of pc. The simulation showed that the intramolecular reaction occurred frequently with increasing the gel fraction beyond the gel point. The structural analysis of the maximum cluster with the computer strongly supported the contribution of the intramolecular reaction to the network formation of the gel.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0959-8103
    Keywords: solution viscosity ; Mark-Houwink-Sakurada equation parameter ; acetylated o-cresol-formaldehyde resin ; unperturbed dimension ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: o-Cresol-formaldehyde resin (OC) and five kinds of acetylated OC (AC-X-OC; X is the degree of acetylation) were prepared. The Θ-temperature for each resin was determined by means of the Shultz-Flory method, and their molecular conformations in both tetrahydrofuran (THF) and Θ-solvent were estimated from the values of the exponents in the Mark-Houwink-Sakurada equations. The effect of the degree of acetylation on the exponent was negligible in THF, but was remarkable in Θ-solvent. In THF, the molecular chains of these resins are relatively extended, because the hydrogen bond between phenolic hydroxyl groups is loosely formed. In Θ-solvent, however, the molecular conformation is compact and the resins are considered to form a pseudo cross-linked network structure through inter- and/or intra-molecular hydrogen bonds. The Mark-Houwink-Sakurada equation for AC-100-OC in 2-ethoxyethanol at 92.0°C was found to be [η]θ = 0.0773 M̄0.50n, where [η]0 is the limiting viscosity number under the Θ-condition, and M̄n is the number-average molecular weight. The unperturbed dimension, (〈r20〉/M̄n)1/2, 〈r20〉 being the unperturbed mean square end-to-end distance, for AC-100-OC was found to be 0.659×10-8 cm g-1/2 mol1/2.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 38 (1989), S. 1305-1312 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of the molecular structure of phenolic resins on the Mark-Houwink-Sakurada (MHS) equation and the conformation in acetone solution were studied. The exponent in the MHS equation was remarkably less than that for linear polymers such as vinyl polymers, cellulose derivatives, and so on. As the cause, the branching and the hydrogen bonding between hydroxyl groups of the neighboring phenolic nuclei were considered. Several kinds of phenol-p-cresol and phenol-p-tert-butylphenol cocondensation resins whose composition differs from one another were synthesized. Despite the difference in the degree of branching, the exponent in the MHS equation for each was approximately equal. On the other hand, the exponent for o-cresol novolak, which was rich in ortho-para methylene linkages was larger than the all-ortho novolak and p-cresol novolak, which were rich in ortho-ortho methylene linkages. Methylation of the phenolic hydroxyl group increased the value of the exponent. From these results, it became obvious that while the hydrogen bonding lowered the exponent in the MHS equation due to molecular conformation compaction in acetone solution, the molecular branching had little effect on the exponent α.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 111 (1968), S. 93-103 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalische Polymerisation von Vinylacetat unter hohem Druck wurde im Bereich von 1-2000 kg/cm2 in Gegaenwart und Abwesenheit von Lösungsmitteln untersucht.Durch den Druck wird das Auftreten von Verzweigunogen bei der Polymerisation in Substanz vermindert; gleicbzeiti nimmt die Kettenlänge des Polyvinylacetates mit steigendem Druck zu.Bei der Polymerisation in Lösung ändert sich die Größe des Aktivierungsvolumens der Kettenübertragung zum Lösungsmittel in der Reihenfolge: Toluol 〉 Chlorbenzol 〉 Brombenzol. In beiden Fällen nehmen die Bruttopolymerisationsgeschwindigkeit und das Molekulargewicht der Polymeren mit wachsendem Druck zu.Das Brattoaktivierungsvolumen der Vinylacetatpolymerisation beträgt -17,4 ml/Mol in Abwesenheit von Lösungsmittel und -12,0 ml/Mol in Benzol.
    Notes: High pressure radical polymerization of vinylacetate with and without solvents has been investigated in the range of 1-2000 kg/cm2.The pressure has the ability to interrupt an occurrence of branching in bulk polymerization and the overall chain length of polyvinylacetate increases with pressure.In solution polymerization, the magnitude of the activation volume of chain transfer to solvent is in following order: toluene 〉 chlorobenzene 〉 bromobenzene. In both cases, the overall rates of polymerizations and the molecular weights of polymers obtained increased with increasing pressure.The overall activation volumes of vinylacetate polymerization are -17.4 ml/mole without solvent and -12.0 ml/mole in benzene.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 111 (1968), S. 104-114 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Radikalpolymerisationen von Itakonsäure wurden unter hohem Druck bis zu 5000 kg/CM2 in verschiedenen Lösungsmitteln untersucht.Injedem der Lösungsmittel wurde der kritische Druck, unter dem die Polymerisation nicht mehr eintritt, bestimint. Es wurde gefunden, daß eine lineare Abhängigkeit zwischen der Dielektrizitätskonstante des Lösungsmittels und dem kritischen Druck besteht. Die Bruttopolymerisationskonstante steigt deutlich mit dem Druck an, und das Aktivierungsvolmen besitzt im Vergleich zu anderen Vinylverbindungen ziemlich große absolute Werte.Die unter hohem Druck erhaltenen Polymeren sind weiß, spröde und schwach hygroskopisch. Sic sind besonders leicht löslich in Wasser, löslich in Methanol und Dimethylformamid; in andern organischen Lösungsmitteln sind sie unlöslich.
    Notes: Radical polymerizations of itaconic acid were investigated under high pressure up to 5000 kg/cm2 in several different solvents.The critical pressures under which polymerization does not take place were determined in each solvent and the relation between the dielectric constant of the solvent and the critical pressure was found to be linear. The overall rate of polymerization increases markedly with pressure and the activation volume indicates fairly large absolute values compared with those of other vinyl compounds.The polymers obtained under high pressure are white and brittle having a somewhat hygroscopic property, are soluble in methanol, dimethylformamide and especially in water, and are insoluble in other organic solvents.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 675-682 
    ISSN: 0887-624X
    Keywords: phenol-formaldehyde resin ; all-ortho oligomer ; intrinsic viscosity ; hydrogen bonds ; pseudo-cyclic conformation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three kinds of all-ortho methylene-linked phenolic oligomers, i.e., 4-tert-butylphenol (BP), phenol (AO), and O-methylated BP (BPM), were prepared with good yields and their dilute solution properties were studied. In acetone, all of these oligomers are highly solvated and molecularly dispersed. In chloroform, however, AO and BP molecules strongly form hydrogen bonds among themselves. By intramolecular and intermolecular hydrogen-bondings, a large portion of the dimers and the trimers of AO and BP associate to form bimolecular aggregates in chloroform, assuming pseudo-cyclic conformations analogous to calix [4] arene and calix [6] arene, respectively. By intramolecular hydrogen-bonding, the tetramers and the hexamers also form pseudo-cyclic conformations by themselves in chloroform. © 1993 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 687-693 
    ISSN: 0887-624X
    Keywords: phenolic oligomer ; metal cation extraction properties ; alkali cation ; alkaline earth cation ; affinity ; selectivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of ethyl acetate (nBP-Es) and trioxyethylene ether (nBP-OE) derivatives of linear all-ortho methylene-linked oligomers of p-tert-butylphenol (n = 1-7) were prepared, and cation extraction properties were determined. For alkali metal cations, nBP-Es showed the affinity, and especially 5BP-Es showed the selectivity for Na+. On the other hand, nBP-OE also showed sufficient affinity; however, the extraction behavior was completely different from that of nBP-Es, that is, the affinity of even membered BP-OE was higher than that of the odd membered. nBP-Es extracted cations by forming a cavity winding around them, while nBP-OE extracted with two trioxyethylene chain picking up cations. For alkaline earth metal cations, nBP-Es extracted more than that for alkali cations. Particularly, 7BP-Es showed the highest affinity for larger cations, Sr2+ and Ba2+, among phenolic oligomers and 18-crown-6 compound. On the other hand, nBP-OE showed a lower affinity than that for alkali cations. It was concluded that the linear phenolic oligomers extracted alkali and alkaline earth metal cations and the kind of ion ligand introduced influenced the affinity and the selectivity. © 1996 John Wiley & Sons, Inc.
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  • 8
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have shown previously that the N-methylpridyl group vibrations of water-soluble porphyrins, M(TMpy-P4), are shifted to lower frequencies (0.5-2.6 cm-1) as a result of coulombic interaction between the N+-CH3 group of M(TMpy-P4) and the PO2 group of a nucleic acid. We have now turned over our attention to the effect of this coulombic interaction on the PO2 group vibrations of nucleic acids. Using Fourier transform ir and Raman spectroscopy, we found that the νa(PO2) at 1221 cm-1 is shifted 12 ∼ 17 cm-1 to higher frequencies, whereas the νs(PO2) at 1087 cm-1 is shifted 18 ∼ 26 cm-1 to lower frequencies, when DNA is mixed with M(TMpy-P4). These results indicate that the N+-CH3 group of M(TMpy-P4) interacts preferentially with one of the two oxygen atoms of the PO2 group of the DNA duplex.
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  • 9
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High molecular weight novolaks were prepared by polycondensation of phenol with paraform-aldehyde in acetic acid. The novolak contains soluble, high molecular weight fractions (Mw ≥ 106). The Θ-temperature of the acetylated novolak was determined in 2-ethoxyethanol according to the Shultz-Flory method. The solution viscosity of acetylated and deacetylated novolaks in THF at 25°C and in a Θ-solvent (2-ethoxyethanol at 105°C) was measured, and the molecular dimension in solution was estimated from the parameters of the Mark-Houwink-Sakurada equation. The exponent of 0.24 in THF (good solvent) for acetylated novolak is equal to that in the Θ-solvent. This suggests that the conformation of the novolak is compact like a sphere both in the good and the Θ-solvent. The theoretical value of the exponent in the MHS equation for highly branched polymers is between 0.2 and 0.25 in a Θ-solvent. The exponent for acetylated novolak in the Θ-solvent is close to this value. It is suggested that the acetylated novolak behaves like a highly branched polymer in a Θ-solvent. The 13C NMR spectrum of novolak confirms that the novolak molecule is a highly branched polymer.
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  • 10
    Electronic Resource
    Electronic Resource
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Rapid Communications 3 (1982), S. 705-707 
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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