Aromatic Polyethers based on Meta-activated Dinitrocompounds

Abstract

Aromatic polyethers containing phenyl sulfone side groups were prepared using aromatic nucleophilic nitrosubstitution reaction. As starting compounds TNT-derived 3,5-dinitrodiphenyl sulfone and 4,4′-bis-[(3-nitro-5-phenylsulfonyl)phenylsulfonyl]diphenyl sulfone containing functional nitro groups activated with electron-withdrawing phenylsulfone meta-substituents were used. Polymers obtained are soluble in wide range of organic solvents and demonstrate large ‘windows’ between their softening and degradation temperatures.

New Sulfonated Polyethers and Polynaphthylimides based on TNT Derivatives

“…Attempts to use 3,5-dinitrodiphenyl sulfone-4 1 -sulfonic acid were more successful because of the electron-withdrawing nature of sulfone "bridging" groups. Generally, electron-withdrawing groups should be located in para-or ortho-positions relative to nitro groups, activating the electrophilic centers by decreasing the electron density on the ipsocarbon atoms1 in addition, the activating groups stabilize the Meisenheimer anionic intermediate complex [12]. In principle, very strong electron-withdrawing groups in the meta-positions to the reaction center can cause sufficient activation of the centers for participation in aromatic nucleophilic substitution reactions [13]1 however, only a few examples of using this concept in polymer synthesis are known [6,12,13].…”

“…Generally, electron-withdrawing groups should be located in para-or ortho-positions relative to nitro groups, activating the electrophilic centers by decreasing the electron density on the ipsocarbon atoms1 in addition, the activating groups stabilize the Meisenheimer anionic intermediate complex [12]. In principle, very strong electron-withdrawing groups in the meta-positions to the reaction center can cause sufficient activation of the centers for participation in aromatic nucleophilic substitution reactions [13]1 however, only a few examples of using this concept in polymer synthesis are known [6,12,13]. Sulfonated aromatic polyethers demonstrating relatively high solution viscosities (2 red up to 0.40 dL g 51 ) were prepared by the interaction of 3,5-dinitrodiphenyl sulfone-4 1sulfonic acid potassium salt with potassium salts of different bis-phenols at 180 4 C for 10 h (scheme 5).…”

Poly(arylene ether)s with Low Refractive Indices: Poly(biphenylene oxide)s with Trifluoromethyl Pendant Groups via a Meta-Activated Nitro Displacement Reaction

“…Therefore, activating groups at the ortho or para position are generally required to obtain high-molecular-weight polymers. Since we first succeeded in making linear poly(arylene ether)s via a meta -activated S N Ar reaction, some examples of the meta -activated S N Ar reaction have been reported to make linear polymers − as well as hyperbranched polymers. , …”