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  • 1995-1999  (12)
  • 1985-1989  (7)
  • 1
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The concentration of propagating radicals during the free radical polymerization of methyl methacrylate in bulk to high conversion at 60°C was determined — (1) by “in situ” measurements in the spectrometer, and (2) using a cryogenic quenching procedure. The radical concentration showed a sigmoidal relationship with polymerization time, and the conformation of the radical was different below and above the gel point of ca. 30% conversion. A value of kt=2.5 (±0.3)×107 1 mol−1 s−1 was obtained below the gel point. The variation in kt, without allowance for a decreasing efficiency factor (f), was determined over the entire conversion range.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1627-1633 
    ISSN: 0887-624X
    Keywords: hyperbranched macromolecule ; polyester ; focal point groups ; intramolecular cyclization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of monomer structure and catalyst on the synthesis of hyperbranched polyesters based on 4,4-(4′-hydroxyphenyl)pentanoic acid has been examined. The nature of the ester group and the catalyst have a significant effect on the molecular weight of the hyperbranched polyester but do not effect the degree of branching for these materials. The fate of the single ester group at the focal point of these hyperbranched macromolecules is probed by the synthesis and polymerization of 13C labeled methyl 4,4-(4′-hydroxyphenyl)pentanoate. Comparison of the molecular weights determined by 1H- or 13C-NMR spectra with those determined by osmometry suggest that intramolecular cyclization does not occur to a significant extent in these systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1627-1633, 1997
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 3089-3099 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESR spectra of gamma irradiated annealed and quenched forms of polypropylene film have been studied at the temperatures used for post-irradiation grafting experiments with butadiene, described in Part I. On warming from low temperature there is radical loss by termination and some radical transformation to radicals with optimum stability in annealed polypropylene at approximately 45°C. These radicals, which may be allyl type, are sited at the crystal faces, and decay more rapidly at higher temperatures in annealed polypropylene; in quenced polypropylene their concentration never exceeds one third the optimum observed in annealed polypropylene. Correlation with the grafting experiments suggests that allyl radicals are important for long-term grafting. Effects on the ESR spectrum of adding butadiene to the system show that in the long-term butadiene adds exclusively to the allyl radicals and that alkyl radicals still present at that stage are precursors to the allyl radicals. They do not react directly with butadiene presumably because they are sited in the inaccessible crystal core. Experiments at lower temperature show that butadiene does react with alkyl radicals in accessible regions.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    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.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 3379-3390 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Syndiotactic poly(2-methylheptyl methacrylate) which was γ-irradiated at room temperature to a dose of 1600 kGy was investigated by NMR spectroscopy. The 1H and 13C resonances for the macromolecular chain were assigned by using the 2D and the DEPT (distortionless enhancement by polarization transfer) technique. The spin-echo modified 2D NMR pulse sequence was used to investigate the small molecules and new structures which were formed during γ-irradiation. The radiation mechanisms for cleavage of the side chain from the main chain and formation of double bonds from both the main chain and the side chain have been formulated based upon the NMR analysis.
    Additional Material: 8 Ill.
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  • 8
    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: UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge-transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-centered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was twofold higher than for vacuum irradiation and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C—O binding energy peak relative to the C—C peak was believed to be associated with an aromatic ring-opening reaction. © 1995 John Wiley & Sons, Inc.
    Additional Material: 13 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 59 (1996), S. 589-597 
    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 γ irradiation of poly(methacrylate)s with various ester groups at room temperature was investigated by gel permeation chromatography and NMR techniques. The G values for scission and crosslinking for each of the polymers were estimated from the changes in the molecular weights and molecular weight distributions. The new structures formed during γ irradiation were examined by 1H-NMR spectroscopy. All of the investigated poly(alkanemethacrylate)s were found to produce the alkane formates during γ irradiation, and for poly(2-methyl heptyl methacrylate) G(S) was less than 4G(X), indicating gel formation in this polymer. In the investigation of poly(benzyl methacrylate), no formate ester was found, but some small molecule compounds formed from the benzyl radical were detected. The benzyl group was also found to stabilize the polymer against radiation damage. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 10
    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 effect of atomic oxygen flux and VUV radiation alone and in combination on the surface of fluorinated polyimide films was studied using XPS spectroscopy. Exposure of fluorinated polyimides to VUV radiation alone caused no observable damage to the polymer surface, while an atomic oxygen flux resulted in substantial oxidation of the surface. On the other hand, exposure to VUV radiation and atomic oxygen in combination caused extensive oxidation of the polymer surface after only 2 min of exposure. The amount of oxidized carbon on the polymer surface indicated that there is aromatic ring-opening oxidation. The changes in the O1s/C1s, N1s/C1s, and F1s/C1s ratios suggested that an ablative degradation process is highly favorable. A synergistic effect of VUV radiation in the presence of atomic oxygen is clearly evidenced from the XPS study. The atomic oxygen could be considered as the main factor in the degradation process of fluorinated polyimide films exposed to a low earth orbit environment. © 1995 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
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