Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method

Abstract

The invention provides a clean, environmentally-friendly and economic bisphenol fluorene synthesizing method, and relates to the field of preparation and organic synthesis of bisphenol fluorene monomers. The method comprises the following steps of: (1) preparation: synthesizing bisphenol fluorene by using cheap 9-fluorenone serving as a starting raw material and phenol in the presence of an acid catalyst and a thiohydracrylic acid cocatalyst; and (2) post treatment: adding a weak base salt to neutralize the catalyst, adding an organic solvent for dissolving, filtering, collecting an organic phase, and reclaiming the solvent and the redundant phenol under reduced pressure. The method is few in reaction steps and easy to operate, the reaction time is shortened, the production efficiency is greatly improved, and industrialized production is facilitated.

Description

technical field

[0001] The invention relates to the field of bisphenol fluorene monomer preparation and organic synthesis, in particular to a clean, environmentally friendly and economical synthesis method of bisphenol fluorene. Background technique

[0002] Bisphenol fluorene, namely 9,9-bis(4-hydroxyphenyl) fluorene, is a fluorenyl compound containing a phenolic hydroxyl structure, soluble in monocyclic and bicyclic aromatic hydrocarbons, acetonitrile, toluene, methanol, dichloromethane and dichloromethane Organic solvents such as ethyl chloride. The preparation of bisphenol fluorene is obtained through the condensation reaction of fluorenone and phenol under the action of a catalyst. In the modern polymerization processing industry, bisphenol fluorene is widely used in condensation reaction, it is an important unit for the synthesis of polycondensation products such as epoxy resin, polycarbonate and polyester with high heat resistance, good optical properties and high fl...

Examples

Embodiment 1

[0037] Add 5.40g fluorenone, 11.29g phenol, 0.10g mercaptopropionic acid into a 100ml four-necked flask equipped with magnetic stirring, mix and stir, and add 1.48g concentrated sulfuric acid dropwise at 55°C for about 0.5h, dropwise After completion, heat up to 60°C, react for 3h, stop the reaction, add 2.60g of anhydrous sodium acetate, stir for 1h, add 20mL of dichloroethane to dissolve, filter, and distill the filtrate under reduced pressure. ), the dichloroethane fraction was collected at 85-100°C (vacuum: 0.09Mp), the acetic acid fraction was collected at 125-150°C (vacuum: 0.09Mp~0.1Mp), and the distillation was completed, weighing About 5.13g of phenol fraction was obtained, and the recovery rate of phenol was 90.96%. The crude product was recrystallized with methanol, and dried in vacuo to obtain 10.08g of white solid, yield: 95.89%, purity: 99.68%. 1 H NMR (CDCl 3 , 500MHz, ppm): δ: 4.95 (2H, s, OH), 6.65~7.75 (16H, m, ArH); IR(KBr), v / cm -1 : 3480(O-H), 3063, 3031...

Embodiment 2

[0042] Add 5.40g of fluorenone, 16.90g of phenol, and 0.15g of mercaptopropionic acid to a 100mL four-neck flask equipped with magnetic stirring, mix and stir, and add 1.15g of methanesulfonic acid dropwise at 55°C for about 0.5h , after the dropwise addition, the temperature was raised to 60°C, reacted for 3h, stopped the reaction, added 1.20g of anhydrous sodium acetate, stirred for 1h, added 20mL of dichloroethane to dissolve, filtered, and the filtrate was distilled under reduced pressure, at 40-50°C (vacuum degree : 0.08Mp) to collect the dichloroethane fraction, collect the acetic acid fraction at 85-100°C (vacuum degree: 0.09Mp), collect the phenol fraction at 125-150°C (vacuum degree: 0.09Mp~0.1Mp), and distill Finished, weighed about 9.68g of phenol fraction, phenol recovery rate reached 86.04%, the crude product was recrystallized with toluene, vacuum dried to give 10.17g white solid, yield: 96.75%, purity: 99.53%.

Embodiment 3

[0044]Add 5.40g fluorenone, 16.94g phenol, 0.15g mercaptopropionic acid, 2.28g p-toluenesulfonic acid into a 100ml four-necked flask equipped with magnetic stirring, mix and stir, react at 70°C for 5h, stop the reaction, add 1.10g Sodium acetate in water, stir for 1h, add 20mL dichloroethane to dissolve, filter, distill the filtrate under reduced pressure, collect the dichloroethane fraction at 40-50°C (vacuum degree: 0.08Mp), and collect the dichloroethane fraction at 85-100°C (vacuum degree : 0.09Mp) to collect the acetic acid fraction, and collected the phenol fraction at 125-150°C (vacuum degree: 0.09Mp~0.1Mp). Recrystallized from ethanol, dried in vacuo to obtain 9.97g white solid, yield: 94.95%, purity: 99.17%.

technical field

[0001] The invention relates to the field of bisphenol fluorene monomer preparation and organic synthesis, in particular to a clean, environmentally friendly and economical synthesis method of bisphenol fluorene. Background technique

[0002] Bisphenol fluorene, namely 9,9-bis(4-hydroxyphenyl) fluorene, is a fluorenyl compound containing a phenolic hydroxyl structure, soluble in monocyclic and bicyclic aromatic hydrocarbons, acetonitrile, toluene, methanol, dichloromethane and dichloromethane Organic solvents such as ethyl chloride. The preparation of bisphenol fluorene is obtained through the condensation reaction of fluorenone and phenol under the action of a catalyst. In the modern polymerization processing industry, bisphenol fluorene is widely used in condensation reaction, it is an important unit for the synthesis of polycondensation products such as epoxy resin, polycarbonate and polyester with high heat resistance, good optical properties and high fl...

Examples

Embodiment 1

[0037] Add 5.40g fluorenone, 11.29g phenol, 0.10g mercaptopropionic acid into a 100ml four-necked flask equipped with magnetic stirring, mix and stir, and add 1.48g concentrated sulfuric acid dropwise at 55°C for about 0.5h, dropwise After completion, heat up to 60°C, react for 3h, stop the reaction, add 2.60g of anhydrous sodium acetate, stir for 1h, add 20mL of dichloroethane to dissolve, filter, and distill the filtrate under reduced pressure. ), the dichloroethane fraction was collected at 85-100°C (vacuum: 0.09Mp), the acetic acid fraction was collected at 125-150°C (vacuum: 0.09Mp~0.1Mp), and the distillation was completed, weighing About 5.13g of phenol fraction was obtained, and the recovery rate of phenol was 90.96%. The crude product was recrystallized with methanol, and dried in vacuo to obtain 10.08g of white solid, yield: 95.89%, purity: 99.68%. 1 H NMR (CDCl 3 , 500MHz, ppm): δ: 4.95 (2H, s, OH), 6.65~7.75 (16H, m, ArH); IR(KBr), v / cm -1 : 3480(O-H), 3063, 3031...

Embodiment 2

[0042] Add 5.40g of fluorenone, 16.90g of phenol, and 0.15g of mercaptopropionic acid to a 100mL four-neck flask equipped with magnetic stirring, mix and stir, and add 1.15g of methanesulfonic acid dropwise at 55°C for about 0.5h , after the dropwise addition, the temperature was raised to 60°C, reacted for 3h, stopped the reaction, added 1.20g of anhydrous sodium acetate, stirred for 1h, added 20mL of dichloroethane to dissolve, filtered, and the filtrate was distilled under reduced pressure, at 40-50°C (vacuum degree : 0.08Mp) to collect the dichloroethane fraction, collect the acetic acid fraction at 85-100°C (vacuum degree: 0.09Mp), collect the phenol fraction at 125-150°C (vacuum degree: 0.09Mp~0.1Mp), and distill Finished, weighed about 9.68g of phenol fraction, phenol recovery rate reached 86.04%, the crude product was recrystallized with toluene, vacuum dried to give 10.17g white solid, yield: 96.75%, purity: 99.53%.

Embodiment 3

[0044]Add 5.40g fluorenone, 16.94g phenol, 0.15g mercaptopropionic acid, 2.28g p-toluenesulfonic acid into a 100ml four-necked flask equipped with magnetic stirring, mix and stir, react at 70°C for 5h, stop the reaction, add 1.10g Sodium acetate in water, stir for 1h, add 20mL dichloroethane to dissolve, filter, distill the filtrate under reduced pressure, collect the dichloroethane fraction at 40-50°C (vacuum degree: 0.08Mp), and collect the dichloroethane fraction at 85-100°C (vacuum degree : 0.09Mp) to collect the acetic acid fraction, and collected the phenol fraction at 125-150°C (vacuum degree: 0.09Mp~0.1Mp). Recrystallized from ethanol, dried in vacuo to obtain 9.97g white solid, yield: 94.95%, purity: 99.17%.