Bisphenol fluorene

Another approach to increase the heat distortion temperature is to produce cocondensates of bisphenol A with bishydroxyphenyl fluorene. Some variations of this copolymer had heat distortion temperatures in excess of 200°C and with the potential to be produced at lower cost than such temperature-resistant thermoplastics as polysulphones and polyetherimides. Plans to develop this material were however abandoned when it was found, during trials of test materials, that workers developed skin rashes said to be similar to those encountered on contact with poison ivy. 

N,N-Dimethylacetamide (DMAc), 4-fluorobenzoic acid, 4-fluorobenzoyl chloride, aluminum chloride, 1 -bromonaphthalene, nitrobenzene, ferric chloride, dimethyl sulfone, 4,4 -dihydroxybiphenyl (DHB), and potassium carbonate were obtained from Aldrich and used without purification. 4,4-(Hexafluoroiso-propylidiene)-diphenol (6F-BPA), 9,9-bis(4-hydroxyphenyl)fluorene (HPF), and l,l-bis(4-hydroxyphenyl)-l-phenylethane (Bisphenol AP) were obtained from Ken Seika Corporation and used without purification. 4,4 -Dihydroxydiphenyl sulfone (DHDS) was obtained from Nachem Incorporated and used without purification. 

An aqueous Friedel-Crafts reaction has also been used in polymer synthesis. The acid-catalyzed polymerization of benzylic alcohol and fluoride functionality in monomeric and polymeric fluorenes was investigated in both organic and aqueous reaction media. Polymeric products are consistent with the generation of benzylic cations that participate in electrophilic aromatic substitution reactions. Similar reactions occurred in a water-insoluble Kraft pine lignin by treatment with aqueous acid. A Bisphenol A-type epoxy resin is readily emulsified in aqueous medium with an ethylene oxide adduct to a Friedel-Crafts reaction product of styrene and 4-(4-cumyl)phenol as emulsifier.Electrophilic substitution reaction of indoles with various aldehydes and ketones proceeded smoothly in water using the hexamethylenetetramine-bromine complex to afford the corresponding Z A(indolyl)methanes in excellent yields.InFs-catalyzed electrophilic substitution reactions of indoles with aldehydes and ketones are carried out in water.Enzymatic Friedel-Crafts-type electrophilic substitution reactions have been reported. ... 

Bis-(4-hydrox5 henyl)-fluorene is commercially synthesized by the reaction of phenol with 9-fluorenone, in the same way as the synthesis of bisphenol A proceeds. Hydrogen chloride, 3-mercaptopropionic acid or methanesulfonic acid are used as catalysts. The condensation reaction of fluorenone and phenol in the presence of gaseous hydrogen chloride proceeds with sufficient speed already by 30°C. ° A high purity monomer can be obtained by a two-step purification process. In the first purification step, the crude 9,9-bis-(4-hydrox5 henyl)-fluorene is refluxed in acetonitrile and recrystallized. In the second step, the product is purified by crystallization from a toluene/isopropanol mixture. 

The degree of sulfonation was varied by incorporation of varying amounts of 6F-bisphenol instead of 9,9-bis(4 -hydroxyphenyl)fluorene, and sulfonation under conditions where only the fluorene imits were sulfonated, not the 6F-bisphenol units. HFIOO S-PAEK contains no 6F-bisphenol. HF85... 

The new advanced copolycarbonate resins are a copolymer of bisphenol A and bishydroxyphenol fluorene (BHPF), a fluorenyl derivate. Among the primary features of Inspire resins are equivalent or better heat and inherent ignition resistance without the use of halogens, improved processability, and superior transparency and optical properties when compared to advanced polymers. 

Polymerization of decafluorobiphenyl with the bisphenols was carried out using the following general procedure to a 250 mL round bottom flask was added 11.36 g (0.034 mol) of decafluorobiphenyl, 11.54 g (0.033 mol) of 9,9-bis(4-hydro typhenyl)-fluorene, 105 g DMAc, and 12.2 g (0.090 moD of potassium carbonate. The mixture was stirred at 120 °C under nitrogen for 17 hrs. The mixture was allowed to cool to room temperature and poured into a blender containing 300 mL of water to precipitate the polymer. The polymer was isolated by filtration, washed with water and dried to yield FPAE 2 as a white powder. 

Isopropylidenediphenol (bisphenol-A), kindly supplied by Dow Chemical, was purified by recrystallization from toluene. Tetramethyl bisphenol-A was prepared according to a reported procedure.(6) 4,4-Sulfonyldiphenol (bisphenol-S) and r rr-butylhydroquinone were recrystallized from acetone and ether/hexanes respectively. 9,9 -Bis 4-(hydroxyphenyl) fluorene, a gift from Ken Seika Corporation was used as received. Manganese dioxide was either prepared in the laboratory (7) or procured from commercial sources. All other reagents were used without further purification. 

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