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  • 1
    Electronic Resource
    Electronic Resource
    Polymerization of isobutene using radioactive methyl chloride (1960)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 227-228 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1960.1204514523
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  • 2
    Electronic Resource
    Electronic Resource
    Polymerization of isobutene at ultra low temperatures (1960)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 229-229 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1960.1204514524
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  • 3
    Electronic Resource
    Electronic Resource
    Fundamental studies on cationic polymerizationsParts of this paper have been presented at the IUPAC International Symposium on Macromolecular Chemistry, Montreal, Canada, July, 1961. i. the inversion temperature (1961)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 55 (1961), S. 311-320 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-temperature AlCl3-initiated polymerization of isobutene has been investigated. Direct evidence of the occurrence of chain-breaking reactions is presented. The polymer molecular weight can be affected by changes in reaction temperature between -35 and -78°C. at the same conversion level. The discovery of inversion temperature (Ti) is described. At Ti, the molecular weight becomes independent of monomer concentration. We call Ti the temperature level at which the dependence of product molecular weight on the monomer concentration changes its sign. The inversion temperature has been observed in methyl chloride, ethyl chloride, and vinyl chloride, and vinyl choride diluents. A theory explaining the phenomenon is postulated. It is suggested that competing chain breaking process having dissimilar activation energies determine the molecular weight. Their effects cancel each other at Ti. The previously reported, unusual inverse relation existing between molecular weight and monomer concentration is explained by the concept of Ti.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1961.1205516130
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  • 4
    Electronic Resource
    Electronic Resource
    Poly(vinyl chloride-g-butyl rubber) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 153-157 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene-isoprene charge by a PVC/Et2AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S2Cl2 of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140115
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  • 5
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. VI. Polymerization of styrene with BF3, BCl3, and BBr3Presented in part at the 172nd A.C.S. National Meeting, San Francisco, CA, as Part II of this series (ref. 1). (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2191-2197 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of styrene with BF3, BCI3, and BBr3 coinitiators and CH2Cl2 solvent has been investigated. The effects of temperature, monomer concentration, and the nature of the boron halide on molecular weights, molecular weight distribution, and conversion were determined. Molecular weights were found to decrease in the order BCl3 〉BF3 〉BBr3. This sequence was discussed in terms of system ionicity and counterion stability. The overall energies of activation for polymerization (ΔEDPn) were -1.6 ± 0.3, -1.9 ± 0.8, and -0.9 ± 0.5 kcal/mole for BF3, BCI3, and BBr3, respectively, which indicated similar overall polymerization mechanisms in the range of -20 to -80°C. The predominant molecular-weight-governing event in polymerizations with BCl3, and BBr3 was chain transfer to monomer, whereas with BF3 chain transfer and termination were nearly equal. Chain termination in BCl3-coinitiated polymerizations involves chlorination of the growing polystyryl cation by BCl3OH⊖ and leads to benzylic chlorine termini.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160909
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  • 6
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. III. BCl3 coinitiator for olefin polymerizationFor previous papers in this series, see Kennedy et al. and Feinberg and Kennedy. (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2801-2819 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of isobutylene with BF3, BCl3, and BBr3 coinitiators has been investigated. The polymerization with BCl3 requires the presence of a cationogen, e.g., H2O. The presence of a polar solvent is also necessary. Surprisingly, large quantities of polar solvent are required for effective polymerization. To obtain high conversions, the mixing sequence of the reagents is critical: BCI3 must be added last to charges containing the monomer and H2O in a polar solvent. Ultimate conversions increase by decreasing the temperature. Kinetic termination exists. Experiments with BF3 and BBr3 revealed that polymerizations induced with BF3 proceed in nonpolar and/or polar media. Polymerization stops with BF3 at less than complete conversion (termination exists). In contrast to findings with BCl3, polymer yields with BF3 increase with increasing temperatures. BBr3 is a very inefficient coinitiator, even in the presence of polar solvent, over the -10 to -90°C temperature range. A hypothesis which explains these observations has been developed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151201
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  • 7
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. IV. Elucidation and control of initiation and termination by the help of model experiments (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2869-2892 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proposition that BCl3-coinitiated olefin (isobutylene, styrene) polymerizations terminate by chlorination has been corroborated by model experiments. Key experiments showed that under simulated polymerization conditions neither tert-butyl chloride nor 2-chloro-2,4,4-trimethylpentane reacts with BCl3; that H2O/BCl3 + 2,4,4-trimethyl-1-pentene (TMP) produce 2-chloro-2,4,4-trimethylpentane; and that H2O/BCl3 + isobutylene gives rise to tert-butyl chloride. Extended model studies demonstrated that certain alkyl and benzyl chlorides produce carbenium ions in the presence of BCl3 and that TMP can readily be alkenylated by using 1-substituted allyl chlorides in conjunction with BCl3. These experiments led to the discovery that olefin polymerizations may be initiated by suitable allyl or benzyl chlorides and BCl3. Accordingly, polymerizations of isobutylene have been carried out with RCl/BCl3, where R is allyl or benzyl. These experiments suggest that both controlled initiation and termination, i.e., initiation by alkenylation and termination by chlorination, can be achieved with the allyl chloride/BCl3 initiator system opening new avenues toward the synthesis of asymmetric telechelic polymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151205
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  • 8
    Electronic Resource
    Electronic Resource
    Cationic polymerization with boron halides. V. Synthesis of poly(isobutylene-b-styrene) and poly(styrene-b-isobutylene) (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 243-259 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Block copolymers of isobutylene and styrene, PIB-b-PSt and PSt-b-PIB, have been prepared by a two-step synthesis involving (1) preparation of terminally chlorinated (telechelic) polyisobutylene or polystyrene “prepolymers” by using the H2O/BCl3 initiator system and (2) blocking from these telechelic prepolymers a second polymer segment by using an alkyaluminum, e.g., Et2AlCl coinitiator. The telechelic polyisobutylene and polystyrene contain tertiary and benzylic chlorine termini, respectively. Block copolymer characterization included detailed selective solvent extraction procedures, coupled with GPC determinations, PMR, solubility, and intrinsic viscosity studies. The synthesis of PIB-b-PSt and PSt-b-PIB provides direct chemical evidence for the presence and position of active chlorine termini in BCl3-coinitiated olefin polymerizations.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160123
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  • 9
    Electronic Resource
    Electronic Resource
    New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). XVIII. Epoxy and aldehyde telechelic polyisobutylenes (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2809-2817 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article concerns the synthesis and characterization of new epoxy and aldehyde telechelic polyisobutylenes, that is, and . The synthesis of the epoxy derivative was achieved by quantitative epoxidation of α,ω-di(isobutenyl) polyisobutylene with m-chloroperoxybenzoic acid and that of the dialdehyde by quantitative isomerization of the epoxy termini with zinc bromide. Infrared (IR) and 1H-NMR analysis of these new telechelic polymers and ultraviolet (UV) analysis of the 2,4-dinitrophenylhydrazine derivative of the dialdehyde indicate quantitative conversions and yields, that is, essentially theoretical functionalization (Fn = 1.95 ± 0.05).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170201007
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  • 10
    Electronic Resource
    Electronic Resource
    Synthesis, characterization, and Diels-Alder extension of cyclopentadiene telechelic polyisobutylene. III. Silylcyclopentadiene-telechelic polyisobutylenePart XXXIII of the series “New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator-Transfer Agents (Inifers)”.Parts of this article have been presented at the National Meeting of the American Chemical Society, Kansas City, September 12-17, 1982. (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2973-2986 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Telechelic polyisobutylenes with silylcyclopentadiene termini (CpSi-PIB-SiCp) were prepared, starting with α,ω-di(t-chloro)polyisobutylene and followed by dehydrochlorination, hydrosilylation, and cyclopentadienylation. The prepolymer was characterized and found to have a terminal functionality close to 2.0. Thermal chain extension by Diels-Alder addition of the end groups did not occur, most likely because of fluxional isomerization of the silylcyclopentadiene end groups, confirmed by model studies. Chain coupling of CpSi-PIB-SiCp prepolymers with stoichiometric amounts of bismaleimide gave rise to degrees of extension of more than 11.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170211013
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