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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Tracer diffusion coefficients D* of both components were measured in mixtures of polystyrene (PS) and polymethylstyrene (PMS), a random copolymer from 60 wt.-% of m-methylstyrene and 40 wt.-% of p-methylstyrene. The results are interpreted in terms of the free-volume theory which yields master curves even for “asymmetric” mixtures of oligomer and polymer chains, if D* is drawn versus the distance from the glass transition temperature, T-Tg. Whereas D* was measured by the forced Rayleigh scattering technique, we also studied photon correlation spectroscopy in these mixtures and observed “slow modes” with decay constants that correspond to diffusion coefficients 2-3 decades smaller than the interdiffusion coefficient.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2H spin relaxation times, T1 and T2 and solid echo line shapes were investigated in 2-propanol (2-POH) solutions of poly(butyl methacrylate) (PBMA) in a wide concentration and temperature range, covering the solution, gel and glass states. From the results in deuterated 2-POH-d6 we found that the polymer influence upon solvent mobility is largely suppressed in the gel and glass states in contrast to normal polymer solutions where below the glass transition an increasing amount of solvent slows down with decreasing temperature. From 2H NMR of deuterated butyl side groups in the PBMA-d9/2-POH system we found that the side group motion is anisotropic and largely independent of solvent concentration in the gel and glass states which confirms that polymer-polymer interaction via side group interpenetration should be considered as the main cause for gel formation in this system.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 1445-1454 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Deuteron relaxation times T1 of polystyrenes deuterated at the backbone (PS-d3) and the phenyl ring (PS-d5), respectively, have been measured in solutions of benzene and diethyl malonate as a function of concentration and temperature. We conclude that the motion of the phenyl ring is faster than that of the backbone, the difference being smallest at high temperatures around 180°C. The temperatures dependence is discussed in relation to the activation energies in polystyrene.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2D NMR spectra have been measured at variable temperatures between -100°C and +110°C in a sample of melt crystallized deuterated polyethylene (PE). The line shape could be decomposed into a central part originating from deuterons in the amorphous regions and outer parts from crystalline regions of PE. The “NMR crystallinity” determined from this separation was 72% in agreement with the X-ray crystallinity of 74%. Changes of the crystalline NMR line shape were interperted in terms of oscillations around the chain axis, the r.m.s. oscillation amplitude varying from 5° at 40°C to 12° at 110°C. The central part of the NMR line shape indicates the existence of a “narrow” and a “medium” component due to different motional processes in the amorphous regions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Telechelic α,ω-macrozwitterions  -  narrowly distributed polystyrene chains oppositely charged at each end  -  were synthesized via anionic polymerization using direct functionalization with the initiator and the termination agent. The resulting products were purified (zwitterion content ≥ 0,95) and characterized with gel permeation chromatography, viscometry, static and dynamic light scattering and small-angle neutron scattering. In unpolar solvents as toluene, the polymeric zwitterions form clusters with molecular weights depending on concentration. In the dilute case, the clusters are relatively small and consist of approximately 8 zwitterions. The structure of these clusters is discussed by their scattering behaviour. Above a critical concentration being in the range of 0,05 g/cm3, an infinite aggregate is formed. Zwitterions in N,N-dimethylformamide behave differently: due to the attenuation of dipolar forces, no clusters are formed. In this case, the behaviour in dilute solution can be described by the formation of polymeric rings consisting of one polymer molecule, only.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solutions of chain- (PS-d3) and phenyl ring (PS-d5) deuterated polystyrenes in perdeuterated PS-d8 have been investigated with 1H and 2D NMR relaxation and wide line methods. The intra- and intermolecular parts of the 1H second moments at -100°C are 3,7 G2 and 2,0 G2, respectively, for PS-d3, and 14,7 G2 and ca. 0 G2, respectively, for PS-d5. The intermolecular contribution to the 1H spin lattice relaxation rate, determined at 55 MHz between 150°C and 250°C, is about one third of the total rate in PS-d3, and negligible in PS-d5. We suggest that this contribution is caused by rotational fluctuations of the intermolecular H⃛H vectors. The intramolecular 1H- and 2D-relaxation rates indicate that the phenyl group motion is somewhat faster than the rotational segmental motion of the polymer chain.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 2759-2761 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 188 (1987), S. 2317-2324 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion coefficients D of singly and doubly end-labeled polystyrenes (PS) with molecular weights in the range 6500 ≤ M ≤ 75400 were measured in a PS matrix of molecular weight M′ = 111000, and in matrices with M′ = M. At 212°C, we find no influence of the label. In a power-law description D = D0 · M-α · M′-β we find α = 2,0 for M′ = 111000 and α + β = 2,4 for M = M′. The crossover to Rouse-like behavior for short-M chains is at Me ≈ 18000 for the former (high M′), and at Mc ≈ 33000 in the latter (M′ = M) case. At 185°C, we find a more complex scaling behavior and different D values for singly and doubly labeled PS.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 797-809 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Tracer diffusion coefficients D* of both components were measured in mixtures of polystyrene with poly(o-methylstyrene), poly(p-methylstyrene), and a commercially available random copolymer of p- and m-methylstyrene, respectively. D* values were determined by applying the holographic grating technique where between 5 and 10% of the respective polymer component was labelled at the end group with a photoreactive dye. For molecular weights between 15 000 and 37 000 and temperatures between 175 and 200°C, the D* values differed relatively slightly when compared at equal molecular weight and equal temperature distance T-Tg from the glass transition temperature Tg. The differences were compared with those of monomeric friction coefficients obtained from dynamic mechanical experiments.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 10
    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.
    Type of Medium: Electronic Resource
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