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In many cases, the reaction of the third component with the inactive dye radical regenerates the dye, that is, photobleaching does not occur Other mechanisms have also been proposed for the three-component systems [Padon and Scranton, 1999] More recently, two-component dye systems with organoborates such as tetramethylammonium triphenylbutylborate in place of amines have been found to be highly active in photoinitiation 3-4c-3 Rate of Photopolymerization.

LONG-TERM GOVERNMENT BOND YIELDS, SELECT INDUSTRIALIZED COUNTRIES, 1980-2005

Ri 2fIa 3-50

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where Ia is the intensity of absorbed light in moles (called einsteins in photochemistry) of light quanta per liter-second and f is the number of propagating chains initiated per light photon absorbed. f is referred to as the quantum yield for initiation. The factor of 2 in Eq. 3-50 is used to indicate that two radicals are produced per molecule undergoing photolysis. The factor of 2 is not used for those initiating systems that yield only one radical instead of two. Thus the maximum value of f is 1 for all photoinitiating systems. f is synonymous with f in that both describe the ef ciency of radicals in initiating polymerization. (The reader is cautioned that this de nition of f is not always used. An alternate approach is

FIGURE 9-23: Solder the pots middle terminals together and solder a wire to an outside lug of each, as shown.

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for MMA polymerization due to the presence of intramolecular solvation. Intramolecular solvation involves electron donation from the carbonyl oxygen of the penultimate unit (i.e., the unit just before the end unit of the propagating chain) as shown in XXVIII [Kraft et al., 1978, 1980]. This additional binding of the counterion to the polymer accounts for the low dissociation constant (K < 10 9 ) for polymethyl methacrylate and also poly(2-vinylpyridine) ion

1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 10-yr. av. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 10-yr. av. 2000 2001 2002 2003 2004 Period av.

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pairs [Tardi and Sigwalt, 1972; Van Beylen et al., 1988]. Intramolecular solvation in poly (2-vinylpyridine) involves electron donation from the nitrogen of a penultimate pyridine ring. This effect may also be responsible for the decrease in dissociation constant of the poly(2vinylpyridine) ion pair with decreasing size of counterion in THF. Thus K is 1:1 10 9 , 2:5 10 9 , and 8:3 10 10 for Cs , K , and Na , respectively [Szwarc, 1983]. This is the reverse of the order observed for polystyryl ion pairs in THF. Apparently, smaller counterions t better or more tightly into the intramolecular solvation sphere. 5-3d-3 Degree of Polymerization

The number-average degree of polymerization for a living anionic polymerization is the ratio of the concentration of reacted monomer to the concentration of living ends (Eq. 5-58). For the usual situation where all the initiator I is converted into propagating chain ends, Eq. 5-58 becomes

12.48 15.22 14.26 11.79 12.75 11.04 9.52 9.95 10.22 9.92 11.72 10.85 9.76 8.77 7.85 8.63 8.28 7.50 6.42 5.47 5.69 7.92 5.89 5.78 5.66 5.28 5.08 5.54

Xn 2p M 0 I 0 5-98

2. Turn the trimmer s dial to full resistance (away from an outside soldered lug) and turn the large pot s dial to no resistance (toward an outside soldered lug, see Figure 9-24).

Xn p M 0 I 0 5-99

depending on the mode of initiation. Equation 5-98 applies to polymerizations initiated by electron transfer since each nal polymer molecule originates from two initiator molecules (e.g., one dianionic propagating species is formed from two sodium naphthalenes). Initiation processes other than electron transfer (e.g., alkyllithium) involve one polymer molecule per initiator molecule, and Eq. 5-99 is applicable. For polymerization involving dormant species in equilibrium with ions and ion pairs (e.g., GTP), [I]0 is the sum of the concentrations of ion, ion pair, and dormant species. Narrow molecular weight distributions are obtained for systems with fast initiation and ef cient mixing in the absence of depropagation, termination, and transfer reaction (Eq. 3-230). PDI values below 1.1 1.2 are found for many living polymerizations. The living polymer technique offers a unique method of synthesizing standard polymer samples of known and wellde ned molecular weights. Commercially available molecular weight standards are now

13.79 14.74 12.88 10.81 10.69 10.62 9.87 9.48 9.36 9.58 11.18 11.08 9.92 9.15 7.87 8.05 8.25 8.10 7.09 5.45 4.70 7.97 4.68 4.78 4.83 4.64 4.77 4.74

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