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Amines such as diethylamine, morpholine, pyridine, and N; N; N 0 ; N 0 -tetramethylethylenediamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. Polymerization proceeds rapidly under mild conditions (25 50 C) for phenols cantaining small substituents. Phenols with one or more bulky o-substituents, such as isopropyl or t-butyl, undergo dimerization instead of polymerization (Eq. 2-200). Dimerization is also the major reaction for phenols with two o-methoxy substituents. The amine : cuprous ion ratio and the reaction temperature determine the extent of carbon oxygen coupling (polymerization) relative to carbon carbon coupling (dimerization), probably by affecting the nature of the complex formed among cuprous ion, amine, and reaction intermediate. Higher amine : cuprous ratios and lower reaction temperatures favor polymerization while dimerization is

French political history in the twentieth century was dominated by the world wars that shaped the history of the entire civilized world Victorious at great sacrifice in World War I, France played a passive role in World War II, but nevertheless emerged a part of the victorious alliance France s political instability, recurrent throughout the nineteenth century and, indeed, since Louis XVI, continued throughout the first six decades of the twentieth century This perhaps explains the failure of such a rich and unusually prosperous nation, victorious in its wars and possessed of large physical and financial resources, to maintain the value of its currency During the period 1960 1990, however, France enjoyed a much larger measure of political stability, and this helped to restrain her inflation and sustain the value of the franc Long-Term French Interest Rates.

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favored by higher temperatures and lower amine : cuprous ratios. Phenols with only one ortho substituent undergo branching during polymerization. Polymerization of phenols with only one ortho substituent, and even phenol itself, has been achieved by using sterically hindered amine ligands for the cuprous ion or other catalytic oxidant [Almou et al., 1999; Higashimura et al., 2000a].

2-200

Chart 55 shows decennial averages for long and short interest rates in nineteenth- and twentieth-century France In view of France s turbulent monetary and financial history in the preceding fifty years, it is surprising to find that up to 1960 so little had changed in the structure of French interest rates French rentes fluctuated in the first six decades of the twentieth century within their nineteenthcentury range Both the discount rate of the Bank of France and the open market rate of discount in Paris ranged below their nineteenth-century averages At times, however, the rates alone did not tell the whole story In periods of pronounced inflation, loans at quoted rates could not be readily obtained.

The mechanism of oxidative coupling polymerization of phenols involves the reaction sequence in Eqs 2-201 through 2-205 The copper amine complex functions as a catalyst for the oxidation by oxygen of the phenol to the monomeric phenoxy radical XXXIX The phenoxy radical then undergoes dimerization by carbon oxygen coupling (Eq 2-201) Polymerization proceeds by oxidation of the dimer to the corresponding phenoxy radical (Eq 2-202) followed by carbon oxygen coupling reactions with monomeric phenoxy radical (Eq 2-203) and itself (Eq 2-204) The trimer continues to grow by repeating the oxidation-coupling sequence; the tetramer continues its growth by dissociation (Eq 2-205) into two phenoxy radicals (a monomer and a trimer) that can undergo coupling reactions Growth to high-molecular-weight polymer proceeds by successive oxidation-coupling sequences The polymer from 2,6-dimethylphenol is the commercial product referred to as poly(pphenylene oxide) or PPO The IUPAC name is poly(oxy-2,6-dimethyl-1,4-phenylene).

replaced with solid metal domes. I added a separate toy organ circuit to experiment with polyphony and beat notes (the pulsing you hear when two frequencies are close to the same). Also added were a separate amp and line outputs for recording and amplification. Later I added light-emitting diodes (LEDs) as soon as they hit the consumer marketplace. Yet another version from the same time period was my portable body-contact-only model. Containing eight foil contacts, it could make all kinds of bird and insect noises (see Figure 1-4).

PPO possesses very little measurable crystallinity (Tm 262 267 C, Tg 205 210 C) There is very little neat PPO used commercially because its high melt viscosity makes processing too dif cult The commercially available products are blends of PPO with high-impact polystyrene (HIPS) (polybutadiene-graft-polystyrene) (Some blends with other rubbery polymers are also available) Blending overcomes the processing problem by lowering the melt viscosity and also increases the impact strength However, the continuous use temperature for the blend, referred to as modi ed PPO (trade name: Noryl), is decreased to the 80 110 C range with the speci c use temperature depending on the relative amount of polystyrene Modi ed PPO has close to the lowest water absorption of all engineering plastics, and this imparts excellent electrical properties over a considerable humidity range.

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