Pentad

These observations suggest how the terminal mechanism can be proved to apply to a copolymerization reaction if experiments exist which permit the number of sequences of a particular length to be determined. If this is possible, we should count the number of Mi s (this is given by the copolymer composition) and the number of Mi Mi and Mi Mi Mi sequences. Specified sequences, of any definite composition, of two units are called dyads those of three units, triads those of four units, tetrads those of five units, pentads and so on. Next we examine the ratio NmjMi/Nmi nd NmjMiMi/NmiMi If these are the same, then the mechanism is shown to have terminal control if not, it may be penultimate control. To prove the penultimate model it would also be necessary to count the number of Mi tetrads. If the tetrad/triad ratio were the same as the triad/dyad ratio, the penultimate model is proved. 

This situation can be generalized. If the ratios do not become constant until the ratio of pentads to tetrads is considered, then the unit before the next to last-called the antepenultimate unit-plays a role in the addition. This situation has been observed for propylene oxide-maleic anhydride copolymers. 

The spectrum shown in Fig. 7.5 shows the appropriate portion of the spectrum for a copolymer prepared from a feedstock for which fj = 0.153 It turns out that each polyene produces a set of three bands The dyad is identified with the peaks at X = 298, 312, and 327 nm the triad, with X = 347 367, and 388 nm and the tetrad with X = 412 and 437 nm. Apparently one of the tetrad bands overlaps that of the triad and is not resolved. Likewise only one band (at 473 nm) is observed for the pentad. The identification ol these features can be confirmed with model compounds and the location and relative intensities of the peaks has been shown to be independent of copolymer composition. 

Once these features have been identified, the spectra can be interpreted in terms of the numbers of dyads, triads, tetrads, and pentads ( ) of the butadiene units and compared with predicted sequences of various lengths. Further con sideration of this system is left for Problems 4-6 at the end of the chapter... 

These triads can also be bracketed by two more units to generate 10 different pentads following the pattern established in Table 7.8. It is left for the reader to verify this number by generating the various structures. 

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