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inflation, the discount rate of the Reichsbank rose to 15% in 1931, and the open market of discount rose to 10%. Short-Term German Interest Rates. Short-term German interest rates are presented in Table 69 in three series: (a) the official discount rate of the central bank in terms of annual average and range, 1900 through 1989; (b) the open market rate of discount in Berlin in terms of annual average and highs and lows of monthly averages, 1900 through 1959; and (c) call money in terms of annual average, 1925 through 1944, and 1950 through 1989, with some exceptionally high spot rates in 1923 and 1924. Chart 70 pictures these short-term rates. The chart suggests the following generalizations: German short-term rates were high in the first decade. The discount rate rose above 7% twice, and the open market rate got up to an annual average of 5%. World War I did not bring a rise in short-term interest rates; instead, they were stabilized at 5% or less. In 1920 there was no crisis marked by high rates, such as occurred in England and America; the crisis with its extraordinarily high rates came a few years later. After the inflation, short rates came down briefly in 1927, but quickly rose again and were very high in the early 1930 s. Short-term rates came down in the 1930 s but remained well above American and English short rates. Typically, the discount rate was 4%. Immediately after World War II, short rates rose to 5 or 6%.

kp and kt values are for 60 C unless otherwise noted. The units for kp and kt are L mol 1 s 1 . Ep and Et values are in kJ mol 1 . c Ap and At values are in L mol 1 s 1 . d Data are from Brandrup and Immergut [1989], Brandrup et al [1999], Eastmond [1976a,b,c], and Walling [1957].

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parameters were then calculated in the appropriate manner These values are typical of radical polymerizations The kp value ($103 ) is larger by many orders of magnitude than the usual reaction rate constant (for example, Tables 2-1, 2-2, and 2-10 show rate constants of approximately 10 3, 10 2 , and 10 6 for esteri cation, urethane formation, and phenolformaldehyde polymerization, respectively) Propagation is therefore rapid, and high polymer is formed essentially instantaneously However, the even larger kt value ($107 ) leads to quick termination, low radical concentrations ($10 8 M), and short radical lifetimes The radical lifetime for methacrylamide in these experiments was 262 s, but it can be shorter or longer under other conditions or for other monomers It is interesting to compare the experimental value (8:75 10 9 ) of Ri with the calculated value (8:73 10 9 ) of Rt .

(continued)

The excellent agreement of the two indicates the validity of the steady-state assumption The rate constants for propagation and termination have been determined for many monomers Table 3-11 lists values for some of the common monomers These data were based on rotating sector experiments The monomers have been listed in order of decreasing kp values (which does not necessarily correspond to the exact order of decreasing kt values) The order of kp values is discussed in Sec 6-3b, since kp is a function of both monomer reactivity and radical reactivity The reader is cautioned that there is often a considerable divergence in the literature for values of rate constants [Buback et al, 1988, 2002] One needs to examine the experimental details of literature reports to choose appropriately the values to be used for any needed calculations.

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Apparently different values of a rate constant may be a consequence of experimental error, experimental conditions (eg, differences in conversion, solvent viscosity), or method of calculation (eg, different workers using different literature values of kd for 1=2 calculating Ri , which is subsequently used to calculate kp =kt from an experimental determination of Rp ) A prime purpose of the IUPAC Working Party on Modeling of Kinetics and Processes of Polymerization has been standardization of the experimental conditions and calculation methods for obtaining rate constants and other parameters Table 3-12 shows the PLP-SEC values of the propagation rate parameters for a number of monomers For many monomers there is good agreement between the values obtained from the rotating sector and PLP-SEC methods..

intermolecular forces, for example, polyamides and polyesters, develop suf cient strength to be useful at lower molecular weights than polymers having weaker intermolecular forces, for example, polyethylene Properties other than strength also show a signi cant dependence on molecular weight However, most properties show different quantitative dependencies on molecular weight Different polymer properties usually reach their optimum values at different molecular weights Further, a few properties may increase with molecular weight to a maximum value and then decrease with further increase in molecular weight An example is the ability to process polymers into useful articles and forms (eg, lm, sheet, pipe, ber) Processability begins to decrease past some molecular weight as the viscosity becomes too high and melt ow too dif cult.

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