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(Similar effects are anticipated for basic monomers) Several mechanisms have been proposed to describe the results for nonionizable monomers: radical solvent complexation, monomer solvent complexation, and the bootstrap effect Complexation of the polar solvent with the more polar monomer or radical decreases the reactivity of the more polar monomer or radical The bootstrap effect results from partitioning of the two monomers between the solution and the local feed composition in the domain of the growing polymer radical Copolymers are richer in the less polar monomer for reaction in polar solvents because the local feed composition is richer in the less polar monomer The magnitude of the bootstrap effect can be signi cant depending on the difference in polarity of the two monomers [Coote et al, 1998].

Thus, for 2-hydroxyethylmethacrylate (M1)-t-butyl acrylate (M2), r1 4:35 and r2 0:355 in bulk copolymerization compared to r1 1:79 and r2 0:510 in copolymerization in DMF [Fernandez Monreal et al, 2001] For a comonomer pair with a smaller difference in polarity such as styrene (M1)-n-butyl acrylate (M2), r1 0:865 and r2 0:189 in bulk compared to r1 0:734 and r2 0:330 [Fernandez Garcia et al, 2000] 6-3a-2 Temperature.

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France nineteenth century, 224 229 twentieth century, 475 480, 670, 673 twenty-first century, 670, 673 Germany nineteenth century, 253, 259 264, 505 twentieth century, 505, 512 516, 670, 673, 675 twenty-first century, 670, 673 Holland, 173, 175 Hungary, 674, 675 India, 674 Indonesia, 674 inflation and, 432 433 Ireland, 207 Israel, 674 Italy twentieth century, 670, 673 twenty-first century, 670, 673 Japan nineteenth century, 578, 584 585 twentieth century, 578, 584 585, 670, 673 twenty-first century, 670, 673 Latin America, 674, 675 lowest rates, 568 569 Mexico, 674, 675 Middle Ages, during the, 8 Netherlands nineteenth century, 237 241 twentieth century, 487 492 New Zealand, 591 592 Poland, 674 Russia, 605, 610, 674, 675 Scotland, 207 Singapore, 674, 675 South Africa, 593, 674 South Korea, 674, 675 Sweden, 267 268, 269 Switzerland nineteenth century, 264 267 twentieth century, 528, 529, 670, 673 twenty-first century, 670, 673 term structure of interest rates, 395, 398, 400, 401 404, 408 Thailand, 674 trends in, 565 570

An examination of various compilations of monomer reactivity ratios [Greenley, 1989a, 1999; Young, 1975] shows that r1 and r2 are relatively insensitive to temperature provided that propagation is irreversible. Thus the r1 and r2 values for styrene-1,3-butadiene are 0.64 and 1.4 at 5 C, and 0.60 and 1.8 at 45 C. The r1 and r2 values for styrene methyl methacrylate are 0.52 and 0.46 at 60 C, and 0.59 and 0.54 at 131 C. The monomer reactivity ratio is the ratio of two propagation rate constants, and its variation with temperature will depend on the difference in propagation activation energies according to

r1 ! k11 A11 E12 E11 exp RT k12 A12 6-48

where E11 and A11 are the propagation activation energy and frequency factor for M1 radical adding M1 monomer, respectively, and E12 and A12 are the corresponding values for M1 radical adding M2 monomer. The effect of temperature on r is not large, since activation energies for radical propagation are relatively small and, more signi cantly, fall in a narrow range such that E12 E11 is less than 10 kJ mol 1 for most pairs of monomers. However, temperature does have an effect, since E12 E11 is not zero. An increase in temperature results in a less selective copolymerization as the two monomer reactivity ratios of a comonomer pair each tend toward unity with decreasing preference of either radical for either monomer. Temperature has the greatest

Here s a really cool housing application. As you shop the charity outlets for circuits to bend, you re bound to run into the small voice-changing megaphones meant to make kids sound like robots or parrots, or be just plain louder (what were they thinking ). These are often bendable and in need of a larger housing for added controls. Just waiting for the transformation are any number of two-part water carafes. Some, like the Mr. Coffee carafe shown, are designed to filter water from the top half to the bottom. Building a megaphone circuit into these is usually easy. Mount the electronics in the top with the speaker firing out the bottom of the filter chamber (just cut out the bottom of the actual carafe with a hole saw). Hold the pouring handle instead as you would the handle of a megaphone, and charm the karaoke crowd (see Figure 11-21).

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