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  • 1
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 559-574 
    ISSN: 0449-2978
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The product of the thermal polymerization of ß-carboxymethyl caprolactam has been identified as a poly[(2,6-dioxo-1,4-piperidinediyl)trimethylene]. An indication of various chain conformations has been explained by the possible existence of two different conformations of the dioxopiperidine moiety. One conformation pertains to an equatorial position of the trimethylene moiety with respect to the plane of the imide group. The other is derived from a structural unit in which the trimethylene group is positioned axially to the plane of the ring. While the former conformation has been ascribed to the crystalline modification the latter appears to be the predominant structure of the polymer in formic acid solution as indicated by NMR analysis. In the glassy state the macromolecule is assumed to be composed of segments of either conformation. The unoriented linear polymer crystallizes upon annealing in positively birefringent spherulites. A triclinic unit cell with the following parameters: a = 9.64 A., b = 11.32 A., c = 15.80 A., α = 98°, β = 96°, γ = 114° has been found to contain eight structural units. The calculated density, 1.30 g./cm.3, agrees with experimental data. A crystal structure is proposed on the basis of the x-ray data.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 867-886 
    ISSN: 0449-2978
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Dynamic mechanical measurements were carried out as a function of temperature (-100 to + 180°C) and frequency (3.5 to 110 cps) for a series of aliphatic terpolyamides, nylon 6 and nylon 12. Effect of crosslinking with toluene diisocyanate, of absorbed water, and of frequency are used to estimate the statistical segment length associated with the α′ relaxation. The effects of variations in the aliphatic chain length in the repeating unit on the temperature of the α′ relaxation are examined by means of copolymer rules with a view to explaining the reported insensitivity of the glass transition temperature of these polymers to changes in (CH2)/(amide) group ratio. From the estimated length of the segmental motion associated with the α′ relaxation it is inferred that in a series of polyamides of the type nylon X or nylon X,Y (where X or Y = 3, 4, 5, 6, etc.) there should be a relatively small change in the temperature of the α′ transition for those polyamides having X or Y less than about 45. Experiments which are intended to establish the position of the crystalline α-γ transition are discussed.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1349-1357 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Phenylphosphonyl-N,N′-biscaprolactam (I) and phenylphosphonyl-N,N′-bis(3,5-dimethylpyrazole) (II) were synthesized and found to be very efficient activators for the anionic polymerization of caprolactam when used in combination with strong bases such as sodium caprolactam. Polymers obtained in the presence of I and II had generally higher molecular weights and were less sensitive to thermal degradation upon molding than those whose preparation entailed the use of N-acetyl-caprolactam (III) as an activator. Thermal behavior and tensile properties indicated that the structure of these polyamides differs from that encountered in nylon 6 prepared with conventional anionic catalyst systems.
    Zusätzliches Material: 8 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 845-860 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pure vinylene carbonate polymerizes readily in dimethyl sulfoxide solutions upon initiation by azobisisobutyronitrile (AIBN). The monomer conversion is characterized by a limiting value which appears to be a function of the temperature and the initial concentrations of both the initiator and the monomer. Increasing both initiator concentration and temperature results in higher final conversions, whereas a maximum conversion is indicated for initial monomer concentrations in the range of 80% to 90%. Principal kinetic quantities were found to be adequately represented by the equations kd = 24.3 × 105 exp {-11300/RT} and kp(f/kt)1/2 = 46.3 × 105 exp {-8900/RT} for the temperature range of 50-80°C. The average degree of polymerization was found to be affected by chain transfer to the solvent. A value of 5.8 × 10-4 was determined for the corresponding chain transfer constant.
    Zusätzliches Material: 20 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2769-2773 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of moisture on the glass transition temperature of poly(hydroxy methylene) was investigated by thermal analysis which entailed combinations of DTA and DSC with TGA techniques. As the moisture content increased, the glass transition temperature (Tg) decreased monotonically from a value (Tgo) of 134°C for the dry polymer toward a finite value (Tgt) of about 39°C. This response of Tg to an increase in the moisture content (w) was adequately represented by the general relationship Tg = (ΔTg)0 exp{-[ln(ΔTg)0]w/τwl} + Tgl, recently developed for correlating Tg and moisture content of nylon 6 and and found generally applicable to hydrophilic polymers. With (ΔTg)0 = 95, τ = 0.555, and wl = 0.375, good agreement was found between experimental and calculated values for poly(hydroxy methylene).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3217-3239 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Esterification-hydrolysis and condensation-glycolysis are the principal equilibria entailed in a system comprised of benzoic acid, ethanediol, ethanediol monobenzoate, ethanediol dibenzoate, and water. These equilibria are characterized by three interrelated equilibrium constants that pertain to the hydrolysis of both ethanediol monobenzoate and ethanediol dibenzoate and to the condensation of ethanediol monobenzoate. The rate constants related to these reactions and to the corresponding reverse reactions were all found to be functions of the concentration of carboxy groups. Antimony triacetate, a well-known transesterification catalyst, catalyzed the condensation reaction strongly but did not affect the esterification reaction. Based on a mechanism that entailed the considered three principal equilibrium reactions, a set of both the kinetic and thermodynamic parameters was obtained by a nonlinear regression procedure. With these parameters the nonlinear rate equations were integrated numerically, using the fourth-order Runge-Kutta method. Excellent agreement between the values thus calculated and the experimental data were obtained in all cases except when considerable concentrations of both benzoic acid and ethanediol dibenzoate were present in the system. It has been concluded that in these instances the formation of the dibenzoate is paralleled by a pyrolysis reaction that is strongly catalyzed by carboxy groups.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3241-3254 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The process of esterification of terephthalic acid is characterized by a mechanism that involves three equilibrium reactions. Two are esterification-hydrolysis equilibria entailing the reactions of the two terephthalic acid carboxyl groups with alcoholic hydroxyl groups, whereas the third one is a transesterification-acidolysis equilibrium that is concerned with the reaction between two terminal terephthalic acid moieties. The products of these three interrelated equilibria are terephthalic acid, its monoester and diester, the particular alcohol, and water. The alcohol used in the present study was 2-(2-methoxyethoxy)ethanol. Equilibrium constants and rate constants were developed from experimental data obtained at 230°C. The esterification-hydrolysis reactions were found to be catalyzed by carboxyl groups, and the rate of transesterification was found to be a function of the terephthalic acid concentration. With the constants developed, the system of nonlinear differential equations, as derived from the mechanism postulated, was integrated numerically using the Runge-Kutta method. Good agreement between calculated and experimental values was observed.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 1229-1236 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The glass transition temperature Tg of nylon 6 decreases monotonically toward a finite value Tgl upon increase of the moisture content. The mechanism of this decrease entails the reversible replacement of intercaternary hydrogen bonds in the accessible regions of the polyamide. The limiting glass transition temperature Tgl is approached when the moisture content approaches Wl, which corresponds to the amount of water required for complete interaction with all accessible amide groups. Denoting with Tg0 the glass transition temperature of the dry polymer, the effect of water on Tg is represented by the equation, Tg = (ΔTg)0 exp{-[ln(ΔTg)0]W/τWl} + Tgl, where (ΔTg)0 = Tg0 -Tgl, and τ = W(Tgl+1)/Wl. This equation appears to be generally applicable to hydrophilic polymers, since correspondingly calculated data are also in very good agreement with experimental data for polymers such as nylon 66, poly(vinyl alcohol), and polyN-vinylpyrrolidone. The effect of water of Young's modulus E of nylon 6 is represented by an analogous relationship, and the quantity In[(E-El)/(Tg-Tgl)] is a linear function of the moisture content.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2703-2708 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 873-896 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The peroxidation of caprolactam has been studied at 84°C, 100°C and 120°C. The decomposition of the initially formed ε-caprolactam hydroperoxide was found to be catalyzed by adipic acid monoamide which is formed by hydrolysis of adipimide. This imide results from the decomposition of the hydroperoxide and was found to act as oxidation inhibitor. The molecular weights of the polyamides obtained by polymerizing the peroxidized caprolactam were found to decrease as the extent of peroxidation and thus the concentration of adipic acid monoamide and other decomposition products increased. In all of these polyamides the concentration of acidic functions was appreciably higher than that of the titratable amino endgroups.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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