Polyethers derived from bisphenols and highly fluorinated aromatics

Abstract

SYNOPSISA series of fluorinated aromatic polyethers was synthesized via aromatic nucleophilic substitution of highly fluorinated aromatics ( 1,2,4,5-tetrafluorobenzene, hexafluorobenzene, and decafluorobiphenyl) with bisphenol AF or bisphenol A. Polymerization with 1,2,4,5tetrafluorobenzene was not observed, and polymerization of hexafluorobenzene with bisphenol proceeded only if the potassium carbonate-bisphenol ratio was carefully controlled.The polymer condensed from decafluorobiphenyl and bisphenol AF was prepared in 77% yield with an inherent viscosity of 1.01 dL/g. The polymer prepared from the condensation of decafluorobiphenyl with bisphenol A was obtained in 48% yield with an inherent viscosity of 0.28 dL/g. These polymers were very soluble in common organic solvents, formed clear, colorless films, and were thermally stable (> 450°C by TGA). The fully fluorinated polymer exhibited low water uptake (0.3% ) and dielectric constant (2.17). 0

Synthesis and Characterization of Polymers from Bisphenol Derivatives and Perfluorinated Aromatic Compounds

“…The same reaction was reported in a previous paper, but the reaction was carried out in the presence of K 2 CO 3 to give low yield even though the reaction time was long. 21 Thus, the presence of NaH was important factor to promote the condensation reaction. When DMAc was used as the polymerization solvent, a high molecular weight polymer was obtained in comparison to DMSO.…”

“…PCBAF was synthesized according to a similar reported method 21,22 in the following; a solution of BAF (0.03 mol), n-propylisocyanate (15 mL), and triethylamine (2 mL) in 300 mL of toluene was heated at 110 C for 10 h. The reaction products were evaporated to dryness giving a crude product. Crystallization twice from CH 2 Cl 2 to hexane gave pure PCBAF in 96% yield;…”

“…[14][15][16][17][18][19][20] However, there are few reports on detailed study of the polycondensation of perfluorinated aromatic compounds such as perfluorobiphenyl (PFB) with 2,2-bis(4-hydroxyphenyl) hexafluoropropane (BAF), although a synthesis of the polymers consisting of PFB and BAF has been reported biefly. 21 Moreover, the polymer containing triphenyl methane and tetraphenyl methane was synthesized using isocynatemasked bisphenols. 22 If the polycondensation of these compounds undergoes as shown in Scheme 1, it will be expected to give polymers with thermal resistance and water repellency.…”

Aromatic Polyethers with a 4‐Chloro‐3‐trifluoromethylphenyl Group

“…To avoid the occurrence of the crosslinking reaction resulting from perfluorobiphenyl, a two-step reaction route was used to obtain 3FC-PAE. [21,23] The reaction included deprotonation of the dihydroxyl monomer to form bisphenolate and the subsequent aromatic nucleophilic substitution of fluorine atoms. High molecular weight polymer was obtained after 72 h of polymerization reaction at room temperature.…”

Methylated and Trifluoromethylated Poly(aryl ethers)

“…After the completion of the hydroquinone dianion formation, the reaction temperature was elevated to 190 • C. However, to avoid the occurrence of a cross-linking reaction, the two-step route (Scheme 2) was performed in the case of perfluorobiphenyl. 20 After the completion of the dianion formation, the reaction system was cooled to room temperature, and then the fluoro monomer was added. To obtain the high molecular weight polymers, a long polymerization period was needed.…”