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due largely to differences in coupon and maturity or temporary differences in supply The credit of the Dominion itself has rested more upon the economy of Ontario than has the credit of the government of the United States rested upon the economy of any one state Chart 77 suggests that the trends of Canadian bond yields in the twentieth century ran closely parallel to the trends of bond yields in the United States Canadian yields, however, were almost always higher than US yields Canadian yields fluctuated much more in harmony with American yields than with English yields English yields gained on American yields, especially from 1900 to 1915 and from 1934 to 1975 Canadian yields did not gain on American yields, although the spread widened in periods of high yields During these nine decades, there was a major shift in the relationship of Canadian to English yields.

3-10d 3-10d-1

Rolling Your Own!

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Autoacceleration of the gel effect type is observed for the polymerization of monomers whose polymers are insoluble or weakly soluble in their own monomers. Examples of this type of behavior are acrylonitrile, vinyl chloride, tri uorochloroethylene, and vinylidene chloride [Billingham and Jenkins, 1976; Gromov et al., 1980a,b; Guyot, 1987; Jenkins, 1967; Olaj et al., 1977a,b; Talamini and Peggion, 1967]. Similar effects are observed in other polymerizations when one uses solvents that are nonsolvents for the polymer [e.g., methanol for polystyrene, hexane for poly(methyl methacrylate)]. The accelerative effects observed in these instances of heterogeneous polymerization are similar to the gel effect and are caused by a decrease in kt relative to kp . The growing polymeric radicals become coiled up, since they are essentially insoluble or on the verge of insolubility in the solvent or in their own monomer. Termination between radicals again becomes progressively more dif cult, while propagation may still proceed reasonably well. The reason for the decrease in occlusion or heterogeneous polymerization is probably due more to a decrease in segmental diffusion than to decreased translational diffusion. Although the propagating radical coil size is decreased in the poor reaction medium, unlike homogeneous systems, segmental diffusion is not enhanced, since diffusion must take place in a poor medium.

The Canadian yields, which in the first decade averaged 87 basis points above the English ones, averaged only 15 basis points above the English yields in the 1920 s They averaged slightly below the English yields during the 1940 s, although part of this change may have been due to difference in maturity of the series used During most of the 1950 s, Canadian yields were far below English yields, although in 1955, and briefly again in 1960, the Canadian yields rose to English levels In the 1960 s, these Canadian yields averaged over 100 basis points below English yields, while during the crisis years of the 1970 s, English yields soared, but Canadian yields rose much less and averaged nearly 500 basis points below English yields.

3-10d-2

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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