Polymers, phenylated aromatic oxidation

Poly(N-phenyl-3,4-dimethylenepyrroline) had a higher melting point than poly(N-phenyl-3,4-dimethylenepyrrole) (171° vs 130°C). However, the oxidized polymer showed a better heat stability in the thermogravimetric analysis. This may be attributed to the aromatic pyrrole ring structures present in the oxidized polymer, because the oxidized polymer was thermodynamically more stable than the original polymer. Poly(N-phenyl-3,4-dimethylenepyrroline) behaved as a polyelectrolyte in formic acid and had an intrinsic viscosity of 0.157 (dL/g) whereas, poly(N-pheny1-3,4-dimethylenepyrrole) behaved as a polyelectrolyte in DMF and had an intrinsic viscosity of 0.099 (dL/g). No common solvent for these two polymers could be found, therefore, a comparison of the viscosities before and after the oxidation was not possible. 

The NMR spectra of copolymers prepared by simultaneous oxidation of the two phenols and those prepared by sequential oxidation, in either order, are almost identical. The methyl peak is broadened, as is the peak caused by the protons of the pendant phenyl rings centered at 8 7.20 ppm, and all show the same peaks for aromatic backbone protons in about the same intensity ratios. The polymer obtained by oxidizing a mixture of DMP and the separately prepared homopolymer of MPP with a cuprous bromide-tetramethylbutanediamine catalyst, the procedure considered to have the best chance of producing a block copolymer, was completely random. 

The pyromellitic dianhydride is itself obtained by vapour phase oxidation of durene (1,2,4,5-tetramethylbenzene), using a supported vanadium oxide catalyst. A number of amines have been investigated and it has been found that certain aromatic amines give polymers with a high degree of oxidative and thermal stability. Such amines include m-phenylenediamine, benzidine and di-(4-amino-phenyl) ether, the last of these being employed in the manufacture of Kapton (Du Pont). The structure of this material is shown in Figure 18.36. 

The oxidation of poly(N-phenyl-3,4-dimethylenepyrroline) with DDQ or Pd/C in nitrobenzene gave in a cyclic aromatic amine polymer with repeating pyrrole rings in the polymer backbone. Using Pd/C in... 

Color. All aromatic azopolymers are colored owing to the strongly chromophoric azogroup. Even the azoblock copolymer derived from a phenyl oxide-isophthalamide backbone (discussed earlier) which has only one azogroup per repeat unit of a molecular weight of 3500 is bright yellow. Naturally, the shade of color of individual polymers depends on the structure of the repeat unit as expected, fully conjugated polymers... 

The introduction of alkyl groups onto the benzene rings of aromatic polyamides has proved to impart higher solubility to the polymers. The thermostability of these however is reduced because of insufficient resistance of the alkyl substituents towards oxidation. Some studies have therefore been carried out using aromatic substituted monomers, for instance, phenyl [27], phenoxy and thio-phenoxy [28] substituted diamines, and phenyl [27, 29, 70] and phenoxy [30] substituted diacids. These have been used to prepare polyamides 15. In Table 4... 

Poly(phenylene oxides) are produced by the oxidative coupling of 2,6-disubstituted phenols. The polymers are also known as poly(oxyphenylenes) or poly(phenyl ethers), and, in the case of dimethyl compounds, also as poly(xylenols). Copper (I) salts in the form of their complexes with amines catalyze the reaction. Primary and secondary aliphatic amines must be used at low temperatures, since otherwise they are oxidized. Primary aromatic amines are oxidized to azo compounds, and secondary aromatic compounds probably to hydrazo compounds. Pyridine is very suitable. 

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