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  • 1
    Electronic Resource
    Electronic Resource
    Nonlinear viscoelasticity of polystyrene solutions. II. Non-Newtonian viscosity (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 1577-1589 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The steady shear viscosity η(k) and the stress decay function \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \eta \left({t,k} \right)$\end{document} (the shear stress divided by the rate of shear k after cessation of steady shear flow) were measured for concentrated solutions of polystyrene in diethyl phthalate. Ranges of molecular weight M and concentration c were 7.10 × 105 to 7.62 × 106 and 0.112-0.329 g/cm3, respectively. Measurements were performed with a rheometer of the cone-and-plate type in the range 10-4 〈 k 〈 1 sec-1. The Cox-Merz relation η(k) = |η*(ω)|ω=k was tested with the experimental result (|*(ω)| is the magnitude of the complex viscosity). It was found to be applicable to solutions of relatively low M or c but not to those of high M and c. For the latter η(k) began to decrease at a lower rate of shear than |η*(ω)|ω=k did; the Cox-Merz law underestimated the effect of rate of shear. The stress decay function was assumed to have a functional form \documentclass{article}\pagestyle{empty}\begin{document}$\tilde \eta \left( {t,k} \right) = \sum {\eta _p \left( k \right)e^{ - t/\tau p\left( k \right)} } $\end{document} where τ1 〉 τ2 〉 …, and the values of τ1, τ2 η1 and η2 were determined for some solutions. The relaxation times τ1 and τ2 were found to be independent of k and equal to the relaxation times of linear viscoelasticity. At the limit of k → 0, η1 and η2 were approximately 60 and 20-30%, respectively, of η and the non-Newtonian behavior was due to large decreases of η1 and η2 with increasing k. It was shown that η1(k) may be evaluated from the relaxation strength G1(s) for the longest relaxation time of the strain-dependent relaxation modulus with a constitutive model for relatively high c-M systems as well as for low c-M systems.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.180130810
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  • 2
    Electronic Resource
    Electronic Resource
    Nonlinear viscoelasticity of polystyrene solutions. III. Stress development at the start of steady shear flow and an experimental check of some constitutive models (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1701-1715 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of the shear stress at the start of shear flow at constant rate of shear κ was measured for polystyrene solutions in diethyl phthalate with a cone-and-plate rheometer. Ranges of molecular weight M and concentration c were 3.10 × 106-7.62 × 106 and 0.112-0.329 g/cm3, respectively. The shear stress as a function of time t exhibited a marked maximum at large κ when either M or c was relatively low. When M and c were high, the maximum was broad and low. In a few extreme cases no maximum was observed in the range of κ studied. The constitutive model of Bernstein, Kearsley, and Zapas could describe approximately the shear stresses at a sudden start and on cessation of steady shear flow with a memory function evaluated from the strain-dependent relaxation modulus. The strain dependence of the memory function for solutions of low M or c was approximately expressed as exp{-α|s|} where α is a constant (ca. 0.37) and |s| is the absolute value of shear strain. When M and c were high, the strain dependence was found to be more diffuse and to require several terms if approximated by exponential functions of |s|. The Lodge model based on a strain-rate dependent relaxation spectrum was not able to describe the strain-dependent relaxation modulus as well as the interrelation between shear stresses at a sudden start and a cessation of steady shear flow.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140915
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  • 3
    Electronic Resource
    Electronic Resource
    Anionic copolymerization of optically active α-methylbenzyl methacrylate and trityl methacrylate. I. Reactivity of monomers (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2917-2928 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The monomer reactivity ratios were determined in the anionic copolymerization of (S)- or (RS)-α-methylbenzyl methacrylate (MBMA) and trityl methacrylate (TrMA) with butyllithium at -78°C, and the stereoregularity of the yielded copolymer was investigated. In the copolymerization of (S)-MBMA (M1) and TrMA (M2) in toluene the monomer reactivity ratios were r1 = 8.55 and r2 = 0.005. On the other hand, those in the copolymerization of (RS)-MBMA with TrMA were r1 = 4.30 and r2 = 0.03. The copolymer of (S)-MBMA and TrMA prepared in toluene was a mixture of two types of copolymer: one consisted mainly of the (S)-MBMA unit and was highly isotactic and the other contained both monomers copiously. The same monomer reactivity ratios, r1 = 0.39 and r2 = 0.33, were obtained in the copolymerizations of the (S)-MBMA-TrMA and (RS)-MBMA-TrMA systems in tetrahydrofuran (THF). The microstructures of poly[(S)-MBMA-co-TrMA] and poly-[(RS)-MBMA-co-TrMA] produced in THF were similar where the isotacticity increased with an increase in the content of the TrMA unit.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170927
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  • 4
    Electronic Resource
    Electronic Resource
    Reactivity of methacrylates in anionic copolymerization with methyl methacrylate by n-BuLi (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1161-1174 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomer reactivity ratios, r1 and r2 were determined in the anionic copolymerizations of methyl methacrylate (MMA, M1) with ethyl (EtMA), isopropyl (i-PrMA), tert-butyl (t-BuMA), benzyl (BzMA), α-methylbenzyl (MBMA), diphenylmethyl (DPMMA), α,α-dimethylbenzyl (DMBMA), and trityl (TrMA) methacrylates (M2) by use of n-BuLi as an initiator in toluene and THF at -78°C. The order of the reactivity of the monomers towards MMA anion was DPMMA 〉 BzMA 〉 MMA 〉 EtMA 〉 MBMA 〉 i-PrMA 〉 t-BuMA 〉 TrMA 〉 DMBMA in toluene and TrMA 〉 BzMA 〉 MMA 〉 DPMMA 〉 EtMA 〉 MBMA 〉 i-PrMA 〉 DMBMA 〉 t-BuMA in THF. Except for the extremely low reactivity of TrMA and DPMMA in toluene due to steric hindrance, the order was explained in terms of the polar effect of the ester groups. A linear relationship was found between log (1/r1) and Taft's σ* values of the ester groups, where the ρ* value was 1.1. The plots of log (1/r1) vs. the 1Ha (cis to the carbonyl) and 13Cß chemical shifts of the monomers were also on straight lines. The polymer obtained in the copolymerization of MMA with TrMA in toluene by n-BuLi at -78°C was a mixture of poly-MMA and a copolymer, suggesting that there exist two kinds of growing centers.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130512
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  • 5
    Electronic Resource
    Electronic Resource
    Microstructure of the copolymers of methyl methacrylate with other methacrylates obtained by radical and anionic copolymerizations in tetrahydrofuran (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1215-1225 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomer reactivity ratios r1 and r2 were determined in the copolymerizations of methyl methacrylate (MMA, M1) with 1, 1-diphenylethyl (DPEMA), α,α-dimethylbenzyl (DMBMA), tert-butyl (t-BuMA), diphenylmethyl (DPMMA), phenyl (PhMA), and 1-naphthyl (NpMA) methacrylates (M2) in tetrahydrofuran (THF) by azobisisobutyronitrile (AIBN) at 60°C and butyllithium (n-BuLi) at -78°C. The reactivities of the monomers were explained in terms of the polar effect of the ester groups in both copolymerizations. All the copolymers isolated in low yields were converted to PMMA either directly or by copoly(MMA - methacrylic acid) to determine the triad tacticities of the copolymers. Coisotactic parameters σ12 and σ21 were determined by assuming the terminal model statistics. The σ21 values always accorded to the σ21 values within experimental error, and in radical copolymerizations they were between isotactic parameters σ11 and σ22 of the homopolymerizations of MMA and M2 monomers. In anionic copolymerizations, however, the σ12 = σ21 values varied, depending on the M2 monomers. In copolymerization with DPEMA the values were less than both σ11 and σ22 with DMBMA they were between σ11 and σ22, with DPMMA, nearly equal to σ11, and with PhMA and NpMA, greater than both σ11 and σ22. The application of these parameters to copolymerizations performed at high conversion was also investigated.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170424
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