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  • 1
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. IV. Cyclopolymerization of diallyl maleate (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 4089-4098 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of diallyl maleate is kinetically discussed in terms of cyclopolymerization using 2,2′-azobisisobutyronitrile as an initiator and benzene as a solvent at 60°C. Thus, the kinetic equations involving bicyclo-intramolecular cyclization are derived by assuming steady-state conditions for the different types of radicals, and various parameters involved in the equations are then estimated approximately from an extension of the corresponding model experimental results. The validity of these treatments is confirmed from the comparison with the experimental data including the relationships between the contents of the unreacted allylic and maleic double bonds and the monomer concentrations. In addition, the sequence distribution of the structural units of the polymer produced is discussed; for example, the content of the bicyclic structural units is estimated to be 47.2% at a 10% dilution of the pure monomer.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170171228
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  • 2
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. IX. Controlled ring closure in the radical cyclopolymerization of allyl methacrylate (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3207-3217 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical cyclopolymerization of allyl methacrylate (AMA) was investigated in detail, especially under the specified conditions; that is, above the ceiling temperature for a head-to-tail propagation (ΔGht ≥ 0) in the polymerization of methacrylate. Thus the structure of the polymer obtained was examined by 1H- and 13C-NMR and infrared (IR) spectroscopy; no existence of unreacted pendant methacrylyl groups was observed, which suggests that, as a cyclopolymerization mechanism of AMA, intermolecular propagation of growing radicals, followed by intramolecular cyclization or intermolecular propagation of the resulting uncyclized methacrylyl radical, occurs exclusively with methacrylyl group. Temperature dependency of cyclization constant Kc was unusual; Kc increased rapidly at elevated temperatures and no linear relationship of ln Kc vs. 1/T was observed. Five-membered ring formation was favored at an elevated temperature and diluted monomer concentration. These results are discussed thermodynamically in terms of controlled ring closure in cyclopolymerization.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170201116
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  • 3
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. II. Effect of alkyl substituent on the cyclopolymerization of alkyl allyl maleates (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2695-2699 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170161027
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  • 4
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. VIII. Highly enhanced polymerizability of allyl maleates by the use of morpholineFor Part VII see ref. 9.Part of the Doctoral dissertation of K. Urushido, Kansai University, March 1980. (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 19 (1981), S. 59-63 
    Details
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.130190204
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  • 5
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. I. Cyclopolymerization of methyl allyl maleate (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 1081-1091 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of methyl allyl maleate is kinetically discussed in terms of cyclopolymerization using 2,2′-azobisisobutyronitrile (AIBN) as an initiator and benzene as a solvent at 60°C. The ratios of the rate constants of the unimolecular cyclization reaction to those of the bimolecular propagation reaction of the uncyclized allyl and vinyl radicals, KA and KV, are estimated to be 9.7 and 1.35 mole/liter by fitting the kinetic equations obtained here to the dependence of the degree of cyclization on monomer concentration, respectively; the large difference between KA and KV is also discussed in detail. On the basis of these results the formation mode and the sequence distribution of the structural units of the polymer produced are discussed in detail; thus, for the polymer obtained in the bulk polymerization, about 90% of the cyclic structures can be formed via the intramolecular attack of uncyclized allyl radical on maleic double bond and the probability of succession of the cyclic structural units in diad sequence is exemplified as 0.27.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160518
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  • 6
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. VI. Cyclopolymerization of diallyl fumarate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1131-1138 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180333
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  • 7
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. V. Cyclopolymerization of methyl allyl fumarate (1980)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1771-1785 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of radical polymerization of methyl allyl fumarate (MAF) is discussed in terms of cyclopolymerization and compared with the polymerization results of methyl allyl maleate (MAM) as a cis isomer. In the polymerization of MAF, the rate and degree of polymerization were quite enhanced compared with MAM, and gelation occurred at low conversion. The content of the unreacted allylic double bonds of the MAF polymer was quite large; whereas those of the unreacted fumaric double bonds and the cyclic structural units showed reverse tendencies. Only a slight presence of a five-membered ring was observed in the MAF polymer. The cyclization constants KA and KV, the ratios of the rate constants of the unimolecular cyclization reaction to those of the bimolecular propagation reaction of the uncyclized allylic and fumaric radicals, were estimated to be 2.73 and 1.48 mole/liter, respectively. These values suggest the great difference in the cyclopolymerization behavior between two isomeric monomers. These results are discussed in detail in connection with the high reactivity of the fumaric double bond compared to the maleic double bond. In addition, the formation mode and the sequence distribution of the structural units of the polymer produced are discussed on the basis of these analytical results. Thus, for the MAF polymer obtained in the bulk polymerization, about 60% of the cyclic structure can be formed via the intramolecular attack of the uncyclized fumaric radical on the allylic double bond, as opposed to the case of MAM via the predominant intramolecular attack (ca. 90%) of the uncyclized allylic radical on the maleic double bond; these results and the low probability for the succession of cyclic structures and the rather high probability of a vinyl-to-vinyl addition are presented.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1980.170180611
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  • 8
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids. VII. Copolymerization of methyl allyl maleate and fumarate with styrene (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 245-256 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical copolymerizations of methyl allyl maleate (MAM) and methyl allyl fumarate (MAF) with styrene (St) are carried out in bulk using AIBN as an initiator at 60°C, and their copolymerization behaviors are compared in detail. The different rate features are observed with each other; thus in the MAF-St copolymerization the rate was quite enhanced and, also, the maximum rate was found at the molar ratio of 1:1 in the monomer feed, whereas no maximum phenomenon of the rate was apparent for the MAM - St copolymerization. The copolymerizability of MAF with St was quite high, whereas that of MAM was very poor. The cyclization of MAM or MAF was hindered by the highly reactive St monomer. These results are discussed in terms of the formation of the charge - transfer complex between MAF and St and, furthermore, the cyclocopolymerization kinetics involving the 17 elementary reactions as the propagation reactions.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190203
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  • 9
    Electronic Resource
    Electronic Resource
    Polymerization of allyl esters of unsaturated acids, 12Part 11: cf.11. Cyclopolymerization of methyl 2-methylallyl fumarate (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 711-721 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of radical-initiated cyclopolymerization of methyl 2-methylallyl fumarate (MMAF) was investigated and compared with the polymerization results of allyl methyl fumarate (AMF). In the former, the extent of cyclization and five-membered ring formation were enhanced. The cyclization constants KA and KV, the ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized 2-methylallylic and fumaric radicals, were estimated to be 3,1 and 3,0 mol · dm-3, respectively. On the basis of these results the formation mode and the sequence distribution of the structural units of the polymer produced are discussed in detail; the low probability for fumaric vinyl addition and high probability for the succession of cyclic structures are calculated for poly(MMAF) as opposed to those of poly(AMF). The cyclopolymerizability and five-membered ring formation are enhanced at elevated temperature. These results are discussed from the standpoint of the steric effect on cyclopolymerizability.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870401
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  • 10
    Electronic Resource
    Electronic Resource
    Functional metal-porphyrazine derivatives and their polymers, 3.Part 2: cf. Makromol. Chem. 180, 2073 (1979). Catalytic activity of Fe(III)-3,4,3′,4′,3″,4″,3″′,4″′-octacarboxyphthalocyanine for decomposition of hydrogen peroxide (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 565-573 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decomposition reaction of hydrogen peroxide was carried out by using Fe(III)-3,4,3′,4′,3″,4″,3″′,4″′-octacarboxyphthalocyanine (Fe(III)-oaPc) as a catalyst, which has previously been reported by Boston et al. Fe(III)-oaPc is a remarkably effective catalyst for the reaction, compared with hemin, other metal-phthalocyanine compounds, or other iron complexes such as [Fe(III)-(bipy)3]X3. The kinetics of this reaction was also investigated in the pH range 5,5 - 10,5 by measuring the initial velocity, V0, of the increasing concentration of O2 using a Warburg respirometer. The reaction proceeds according the catalase-like mechanism. On the basis of the results of Sigel et al., the reaction mechanism is discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810304
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