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Kress, and J A Osborn, Makromol Chem, 189, 2797 (1988) Gross, R A, Y Zhang, G Konrad, and R W Lenz, Macromolecules, 21, 2657 (1988) Gross, R A, A Kumar, and B Kalra, Chem Rev, 101, 2097 (2001) Grubbs, R H, D A Dougherty, and T M Swager, J Am Chem Soc, 110, 2973 (1988) Gunatillake, P A, G Odian, and D A Tomalia, Macromolecules, 20, 2356 (1987); 21, 1556 (1988)..

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The inherent viscosity Zinh is a measure of the polymer molecular weight. Larger values of Zinh indicate higher molecular weights. Early precipitation of the polyurethane occurs in



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In the later part of the nineteenth century, the hottest new theory in physics was Maxwell's classical electrodynamics. As we know, one of the outstanding features of Maxwell's theory is the prediction that light is an electromagnetic wave. Lord Kelvin's discovery in 1853 of the oscillatory discharge of a Leyden jar [597] gave a way of producing electrical waves. Still, before Hertz's successful experimental

TABLE 2-4 Effect of Solvent on Molecular Weight in Polymerization of Bis(4-isocyanatophenyl)methane with Ethylene Glycola; b Solvent Xylene Chlorobenzene Nitrobenzene Dimethyl sulfoxide Zc inh 0.06 0.17 0.36 0.69 Solubility of Polymer Precipitates at once Precipitates at once Precipitates after 1 h 2 Polymer is soluble





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confirmation of Maxwell's prediction, physicists were eager to study any system producing electrical oscillations So in 1883, 27-year-old J J Thomson 13 set to work on the problem of finding electrical oscillations that can occur on the surface of a conducting sphere 14 Even though he is widely respected now for his achievements in experimental physics, Thomson always had a knack for theory [576] His solution appeared in a paper published in the Proceedings ofthe London Mathematical Society in 1884, the same year he was offered the chair of Cavendish Professor at Cambridge and elected a Fellow of the Royal Society [594] Thomson considered a thin spherical shell and calculated the resulting electromagnetic oscillations when the cause that first produced an irregular charge distribution on the surface of the shell is suddenly withdrawn.

a Data from Lyman [1960]. b Polymerization temperature: 115 C. c Measured in dimethylformamide at room temperature.

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These oscillations are due to the interchange of energy between the currents that start off to cancel the charge distribution and the potential energy of this distribution He looked into two cases: one where the initial irregular charge distribution is created by some electrical system inside the sphere, and another where it is created by a system outside In the latter case, Thomson realized that "since the currents fade away, owing to the resistance of the conductor," the field radiated outside the sphere will be damped In his analysis, this meant that the only solution for the field outside the sphere had to be an outgoing spherical wave So from a physical consideration, Thomson was led to Sommerfeld's radiation condition before Sommerfeld formulated it in all its generality What Thomson calculated were the natural modes of oscillation of his spherical shell "cavity.

xylene and chlorobenzene and limits the polymerization to a low molecular weight. Higher molecular weights are obtained when the solvent for the reaction becomes a better solvent for the polymer. The highest polymer molecular weight is obtained in DMSO (dimethylsulfoxide), a highly polar aprotic solvent, in which the polyurethane is completely soluble during the entire course of the polymerization. Figure 2-7 shows similar behavior for the polymerization between terephthaloyl chloride and trans-2,5-dimethylpiperazine in mixtures of chloroform with carbon tetrachloride or

" These are the modes in which a cavity naturally resonates after the source that drove it initially is suddenly withdrawn They result from a direct application to the case of an open cavity of the physical idea of mode discussed in Section 23 To calculate these modes, one must not only use the boundary conditions on the cavity walls, but also impose Sommerfeld's radiation condition at infinity..

Fig. 2-7 Polymerization of terephthaloyl chloride and trans-2,5-dimethylpiperazine in mixed solvents. After Morgan [1963, 1965] (by permission of Wiley-Interscience, New York).

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n-hexane [Morgan, 1963, 1965] Chloroform is a good solvent for the polymer, while carbon tetrachloride and n-hexane are poor solvents The inherent viscosity of the polymer (measured at 30 C in m-cresol) increases as the reaction mixture contains a larger proportion of chloroform The better the reaction medium as a solvent for the polymer the longer the polymer stays in solution and the larger the polymer molecular weight With a solvent medium that is a poor solvent for polymer, the molecular weight is limited by precipitation Other examples of this behavior are described in Secs 2-8c and 2-14.

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