vb.net ocr read text from pdf

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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

During the bear bond markets of the 1960 s, Canadian yields rose on average somewhat more than did yields in the United States and averaged a wide 68 basis points higher, well above their previous yield premium In the 1970 s, however, Canadian yields rose less than did US yields, and the spread became at times nominal In the 1980 s, the spread between Canadian and American yields widened sharply, while Canadian advantage over Britain nearly disappeared The decennial averages in the table on page 553 illustrate these shifts in international relationships Until the 1980 s, there was little shift in the Canadian-US differential The change that occurred in the Canadian-English differential reflected the change that occurred in the US-English differential The Canadian-US differential, however, was highly variable from year to year.

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Switches are very simple. They just connect or disconnect two wires, usually. If you buy flat, brass-rod stock, you can fashion your own reed switches (no, I can t claim the honor reed as in an elastic tongue of metal ). From brass stock (available at hobby shops), cut two reeds of the same length and solder a wire to an end of each. Wrap 1 2"-wide masking tape around one of the reeds just past the solder until the tape builds up to 1 8" thickness. Hold the remaining reed parallel to the first and wrap the entire unit with tape a few more times. Trim the tape and coat the tape junction with a quick-setting glue such as five-minute epoxy or hot-melt. Any pressure on either reed toward the other will now close the switch and connect the circuit running through this switch (see Figure 6-8). Custom switches like these are nice for unusual applications involving limited space or unordinary, hand-fashioned switch buttons (see the section about Vox Insecta in 11).

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].

The kp = 2kt 1=2 may vary with [M] because changing [M] may change the viscosity and/or goodness of the solvent (which effect the rates of segmental and/or translational diffusion) An increased dependence of Rp on [M] may also result from the second step (Eq 3-14a) of the initiation sequence becoming the rate-determining step, due to decreased mobility of the primary radicals A lower than 1-order dependence of Rp on [I] may be the indirect result of the correspond2 ing change in polymer molecular weight The termination rate constant would decrease with polymer molecular weight, which in turn decreases with initiator concentration, leading to a dependence of Rp on [I] less than 1-order, even 0-order in some instances.

One the other hand, 2 the dependence of Rp on [I] becomes close to rst-order in some heterogeneous polymerizations because the propagating radicals become so coiled up and inaccessible as to be incapable of undergoing termination under the usual reaction conditions [Ueda et al, 1984] Termination becomes rst-order in radical concentration The presence of buried or trapped nonterminated radicals has been shown by ESR and the ability of photochemically produced reaction mixtures to continue polymerizing for days after the discontinuation of illumination [Sato et al, 1984] Such long-lived radicals have been studied as a means of producing block copolymers [Sato et al, 1983; Seymour and Stahl, 1977] Thus, vinyl acetate has been polymerized in a poor and/or viscous solvent to produce occluded macroradicals, which then initiate the polymerization of methyl methacrylate, acrylic acid, acrylonitrile, styrene, and N-vinylpyrrolidinone to produce various block copolymers.

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