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Template (matrix) polymerization involves the polymerization of a monomer in the the presence of a polymer, often a polymer derived from a different monomer [Ciardelli et al., 2001a,b; Gons et al., 1978; Matuszewska-Czerwik and Polowinski, 1990; Polowinski, 2002; Srivstava et al., 1987; Tan and Challa, 1987, 1988; Tewari and Srivastava, 1989; van de Grampel et al., 1988]. The original polymer and formed polymer are often referred to as parent and daughter polymers, respectively. Examples include acrylic acid with polyethyleneimine or poly(N-vinylpyrrolidinone), N-vinylimidazole with poly(methacrylic acid), acrylonitrile with poly(vinyl acetate), and methyl methacrylate with poly(methyl methacrylate). Many of these polymerizations proceed with rate enhancements relative to the corresponding polymerizations in the absence of polymer. The rate enhancements are typically by a factor no larger than 2 5, although a few larger enhancements have been observed. Two types of mechanisms appear to be operative depending on how strongly monomer is absorbed to polymer. A zip mechanism occurs when monomer is strongly complexed with the parent polymer. The complexed monomer molecules are lined up next to each other, which facilitates rapid propagation when an initiating radical from the surrounding solution adds to one of the absorbed monomer molecules. The stereochemistry of the template polymer has an effect on the rate enhancement. For example, the polymerization rate for N-vinylimidazole with poly(methyl methacrylate) template increases in the order: isotactic, syndiotactic, atactic [van de Grampel et al., 1992]. (The meanings of the terms isotactic, syndiotactic, and atactic are discussed in Chap. 8.) The effect of template stereochemistry on polymerization rate varies with the monomer, template polymer, and temperature.





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For monomers that only weakly complex with the parent polymer, polymerization occurs by a pickup mechanism. Initiation occurs in the surrounding solution to form a propagating oligomer that then complexes with the parent polymer. Subsequent propagation proceeds as monomer is picked up at the propagating center. Rate enhancement for zip propagation probably results from an increase in kp due to alignment of monomer molecules on the parent polymer coupled with a decrease in kt due to slower translational and segmental diffusion of propagating radicals. Only the latter effect is operative for template polymerizations involving the pickup mechanism. Template polymerizations have been of interest from the viewpoint of synthesizing stereoregular polymers (Chap. 8) by using a stereoregular parent polymer but this approach has been successful in very few instances. 3-10e Dependence of Polymerization Rate on Initiator and Monomer

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The occurrence of the three stages of homogeneous polymerization and the occlusion and template polymerizations give rise to observed deviations of the usual kinetic expressions (eg, Eqs 3-32 and 3-98) It is not unusual to observe Rp dependence on [M] of greater than rst-order and Rp dependence on [I] of either less than or greater than 1-order (A dif 2 culty in evaluating literature data is that it is not always clear what reaction conditions (stage I, II, or III, occlusion, template ) exist in a particular study) Such results are almost always artifacts For both homogeneous and heterogeneous polymerizations, one may observe a higher than rst-order dependence on [M] due to the kp = 2kt 1=2 ratio varying with [M] to some power, which coupled with the normal rst-order monomer dependence of propagation gives a higher than rst-order dependence of Rp on [M].

as both wand w t do not have a scalar part (Le., no time component). We have a wave equation for a candidate wavefunction of our massive photon, and a four-vector, formed from it, candidate to probability four-current that satisfies a continuity equation. But we have said nothing yet about how observable quantities are to be calculated in this theory. This is a very important point. After all, this is the link between the theoretical framework and experiment. If the timelike component of wtw + f.L2~t~ is to be a probability density, the expectation values of physical observables should be given by the averages of the corresponding operators weighed by this probability density. We will show now that this is so. Using (3.72) and (3.73), we can easily check that for positive-energy solutions,32

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