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The strong dependence of Tc and M c on pressure can lead to the observation of a threshold pressure a pressure below which polymerization does not occur for a particular monomer concentration at a particular temperature. 3-12c Other Effects of Pressure

where 33 G(r[r') = Analogously,



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High pressures also affect the course of polymerization through changes in the physical properties of a reaction system. (The effect of increased viscosity has previously been mentioned.) The freezing point of a liquid usually rises with increasing pressure, about 15 25 C per 100 MPa. Thus increasing pressure may result in changing the state of a reaction system from liquid to solid or the exact nature of the liquid state with corresponding complications in the rate and/or thermodynamics of polymerization [Sasuga and Takehisa, 1978; Weale, 1974]. Dielectric constant also increases with increasing pressure [Ogo et al., 1978]. These changes often lead to discontinuities or changes in the quantitative effect of pressure on rate and degree of polymerization and/or equilibrium constant.

(2'11-)3

3-13





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The conditions under which radical polymerizations are carried out are of both the homogeneous and heterogeneous types. This classi cation is usually based on whether the initial reaction mixture is homogeneous or heterogeneous. Some homogeneous systems may become heterogeneous as polymerization proceeds as a result of insolubility of the polymer in the reaction media. Mass and solution polymerizations are homogeneous processes; suspension and emulsion polymerizations are heterogeneous processes. Emulsion polymerization will be discussed separately in Chap. 4. The other processes will be considered

(3.99)

here. All monomers can be polymerized by any of the various processes. However, it is usually found that the commercial polymerization of any one monomer is best carried out by one or two of the processes. The laboratory techniques for carrying out polymerizations have been discussed [Sandler and Karo, 1992, 1993, 1998; Sorenson et al., 2001]. Up-to-date technological details of commercial polymerizations are dif cult to ascertain, although general descriptions are available [Arpe, 2002; Brydson, 1999; Grulke, 1989; Matsumoto et al., 1977; Menikheim, 1988; Munzer and Trommsdorff, 1977; Salamone, 1996; Saunders, 1988; Schildknecht, 1977].

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(3.100) If it were not for ytk2 + J.L2 in (3.99), G(r[r') would be a three-dimensional delta function and :Fa('R.) and A",('R.) would depend on Woo and ~a, respectively, at the space-time point 'R. only. But as it stands, the fields depend on the wavefunctions in a nonlocal way. This nonlocal dependency implies that the wavefunction can even vanish at a point in space where the energy density does not. So we cannot interpret the scalar component of the quaternion + J.L2~t~ at a point in space as the probability of finding the photon (the energy quantum) at that point,34 Moreover, as we will see in 5, the interaction with an electron, say, at a given point in space depends on the value of the fields at that point. But due to the nonlocal relation between the fields and the wavefunction, this interaction will be nonlocal in the wavefunction. So the electron will interact with the photon even if it sits at a place where the wavefunction vanishes (see Sec. 25(d) in [480]). This difficulty is not present in momentum space, where the fields depend on the wavefunction in a local way. It is perfectly legitimate to talk about the wavefunction of the photon in momentum space [12]. In fact, the photon wavefunction in momentum space is often used in high-energy physics. We can also see immediately that this problem does not exist in the nonrelativistic limit either. For then, the particle's momentum hk is always much smaller than J.L, so that G (r[ r') reduces to .,jii03 (r- r'), making the fields become local in Wand <P.

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