Polymer derived from trichlorophenoxide

Figure 3. C-13 NMR spectra of polymers derived from (a)2-bromo-4,6-dichloro-phenoxide, (b) 4-bromo-2,6-dichlorophenoxide, (c) 2,4,6-trichlorophenoxide 30,000), and (d) 2,4,6-trichlorophenoxide (M = 5,000)...

Figure 5. Effect of added Cr(acac)s on the H-NMR spectrum of polymer derived from 2,4,6-trichlorophenoxide. [Cr(acac)s] = OM (a) 5.7 X (b) 1.2 X...

Chemical analysis of the polymer from 2-bromo-4,6-dichloro-phenoxide revealed that somewhere between one half and two thirds of the available bromine was displaced. The presence of residiaal bromine in the polymer is also manifest by the sharp resonance at 118.6 ppm. This residual bromine is also the lilcely cause of the characteristic difference in the 130 ppm region between polymers derived from 2-bromo-4,6-dichloro (2 peaks) and 2,4,6-trichlorophenoxide (3 peaks). In addition to the units 1 and 2, the 2-bromophenoxide could also contain units 3 and 4. ... 

The advantage of the alternation postulate is that it resolves the anomaly that the deliberate introduction of large numbers of units 1 into polymers derived from either 2,4,6-trichlorophenoxide, or from 2-bromo-4,6-dichlorophenoxide, whilst sharpening the spectra does not radically change the characteristic numbers and positions of the homopolymer resonances. A tendency to alternate would suppress both the generation of longer runs of 1,4-cou-pled units and the e q)ression of the presence of such runs in the and spectra. 

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