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Crosslinking is distinguished by the occurrence of gelation at some point in the polymerization. At this point, termed the gel point, one rst observes the visible formation of a gel or insoluble polymer fraction. (The gel point is alternately taken as the point at which the system loses uidity as measured by the failure of an air bubble to rise in it.) The gel is insoluble in all solvents at elevated temperatures under conditions where polymer degradation does not occur. The gel corresponds to the formation of an in nite network in which polymer molecules have been crosslinked to each other to form a macroscopic molecules. The gel is, in

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3-147

FIGURE C-19

probably a consequence of the transfer reaction (Eq. 3-148) being faster than the reaction in Eq. 3-146; that is, phenols scavenge peroxy radicals more effectively than do alkyl (carbon) radicals. Most phenols have y values close to 3, indicating that the peroxy radical formed in Eq. 3-148 reacts with propagating radicals (carbon and/or peroxy). This probably involves

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Under them, there was often no legitimate capital available for small personal loans to urban workers Many of these workers were driven to illegal loan sharks This was a situation that has been reported repeatedly from the earliest chapters of this history In ancient Babylonia, Greece, and Rome and in Europe during the Middle Ages the provision and regulation of consumer credit was a pressing political and social issue Legislation in the twentieth century has provided for small personal loans through regulated institutions at higher rates of interest than were permitted by the usury laws In addition, purchases of consumer goods may legally be financed at higher rates of interest through sales finance companies, which buy time payment notes at a discount from dealers Effective rates of interest on installment loans in the late 1950 s were permitted up to 12 24% a year.

3-148

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the propagating radical adding to the ring or abstracting hydrogen from a methyl group on the ring for methyl-substituted phenols. In contrast to phenol and substituted phenols, di- and trihydroxybenzenes such as hydroquinone, t-butylcatechol (1,2-dihydroxy-4-t-butylbenzene), and pyrogallol (1,2,3-trihydroxybenzene) are generally stronger retarders or inhibitors. The mechanism for their action may involve oxidation by adventitious oxygen to quinones instead of or in addition to the reactions described by Eqs. 3-147 and 3-148 [Georgieff, 1965]. Substituted anilines behave similarly to the phenols, although relatively little data are available. N-phenyl-N0 -isopropyl-p-phenylenediamine is an ef cient inhibitor in the polymerization of styrene only in the presence of oxygen [Winkler and Nauman, 1988]. However, the effectiveness of phenothiazine as an inhibitor in the polymerization of acrylic acid is independent of oxygen [Levy, 1985]. Aromatic nitro compounds terminate propagating chains, with a greater effect for more reactive and electron-rich radicals. Nitro compounds inhibit vinyl acetate, retard styrene, but have little effect on methyl acrylate and methyl methacrylate [Eastmond, 1976a,b,c; Schulz, 1947; Tabata et al., 1964]. The effectiveness increases with the number of nitro groups on the ring. 1,3,5-Trinitrobenzene has z values that are 1 2 orders of magnitude greater than nitrobenzene (Table 3-8). The mechanism of radical termination involves attack on both the aromatic ring and the nitro group. Attack on the aromatic ring yields radical XXXII, which reacts with another propagating radical (Eq. 3-149) or with monomer (Eq. 3-150).

Commercial banks, likewise, were permitted to extend consumer credit at rates as high as 7 14% (520) and sometimes higher In 1960, statutory limits for interest on the smallest personal finance loans, usually of $300 or less, ranged from 30 to 48% in most American states, with 36% the most common legal maximum The statutory limit for larger loans made by small loan companies, usually about $1000, generally ranged from 8 to 36% per annum Pawnshops in New York were permitted to charge 3% a month for the first six months and 11 2% a month for the next six months, or 27% for the first year In Pennsylvania the pawnshop rate was 3% a month on merchandise and 11 2% a month on jewelry New Jersey permitted 2% a month, or 24% a year.

NO2 + Mn H 3-149

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