1-chloro-4-(4-chlorophenyl)sulfonylbenzene

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A vertical glass tube having a length of 90 cm and a diameter of 4 cm was packed with glass balls and heated at 70° C. 225 g (2.0 moles) of chlorobenzene, 126 g (1.0 mole) of dimethyl sulfate and 160 g (2.0 moles) of sulfur trioxide were simultaneously fed, dropwise, to the top of the tube at approximately the same rates over 30 minutes. Contrary to the procedure adopted in Example 1, the effluent reaction mixture was not immediately precipitated in dilute sulfuric acid but was continuously recycled to the packed column at a pump rate of 2 l/h. Once all of the starting components had been fed to the reactor, recycling was continued at the same rate for a further half-hour, after which the effluent reaction mixture was precipitated in 1 liter of 5% sulfuric acid. Purification was carried out as described in Example 1 to give 261 g (91%) of bis(4-chlorophenyl) sulfone of 97% purity. A vertical glass tube having the effluent reaction mixture was not immediately precipitated in dilute sulfuric acid was continued at the same rate for a further half-hour after which the effluent reaction mixture was precipitated in 1 liter of 5% sulfuric acid Purification

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: When the components are passed once through the reactor at a rate giving a residence time of from 1 to 3 minutes, the conversion rate is 57%. This can be increased to 91% conversion by continuously pumping the effluent reaction mixture back to the fixed bed of the reactor to give an average residence time of approximately 15 minutes. No advantage is gained, we have found, by first converting sulfur trioxide and dimethyl sulfate to reactive dimethyl pyrosulfate and then reacting the latter with chlorobenzene. Precipitating the product in chlorobenzene instead of aqueous sulfuric acid gives bis(4-chlorophenyl) sulfone having a purity of >99.5%. giving a residence time of from 1 to 3 minutes This can be increased to 91% conversion the effluent reaction mixture back to the fixed bed of the reactor to give an average residence time of approximately 15 minutes Precipitating the product in chlorobenzene instead of aqueous sulfuric acid

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: All apparatus is rigorously dried and flushed with nitrogen before use. The reaction is performed in a 250 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. The flask is charged with 3-trifluoromethyl-phenol (11.29 g, 69.7 mmol), 4,4'-dichlorodiphenyl sulfone (10.00 g, 34.8 mmol), K2CO3 (15.00 g, 109 mmol) and DMF (125 mL). The reacting mixture is stirred and heated at reflux for 12 hours. The mixture is analyzed by gas chromatography, which showed that almost no starting materials remained. The reaction mixture is diluted with water, and the aqueous layer is removed to leave an oil. This oil is diluted with ether and washed with 5% NaOH to remove any acidic species. It is then washed with brine, dried with MgSO4, and the solvent removed on the rotary evaporator to leave a white crystalline solid. This solid is purified by column chromatography on flash grade silica gel using a 1:1 mixture of CH 2 Cl2 /Hexane as eluent. Further purification is accomplished by recrystallization of the white solid from ethanol to give white, diamond-shaped crystals (11.08 g, 59%), m.p. 96.5-97.5° C. All apparatus is rigorously dried flushed with nitrogen before use The reaction is performed in a 250 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube heated at reflux for 12 hours the aqueous layer is removed to leave an oil washed with 5% NaOH to remove any acidic species It is then washed with brine dried with MgSO4 the solvent removed on the rotary evaporator to leave a white crystalline solid This solid is purified by column chromatography on flash grade silica gel using a 1:1 mixture of CH 2 Cl2 /Hexane as eluent Further purification is accomplished by recrystallization of the white solid from ethanol to give white

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: All apparatus is rigorously dried and flushed with nitrogen before use. The reaction is performed in a 250 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube, and a stopper. The flask is charged with 3-trifluoromethyl-phenol (11.29 g, 69.7 mmol), 4,4'-dichlorodiphenyl sulfone (10.00 g, 34.8 mmol), K2CO3 (15.00 g, 109 mmol) and DMF (125 mL). The reacting mixture is stirred and heated at reflux for 12 hours. The mixture is analyzed by gas chromatography, which showed that almost no starting materials remained. The reaction mixture is diluted with water, and the aqueous layer is removed to leave an oil. This oil is diluted with ether and washed with 5% NaOH to remove any acidic species. It is then washed with brine, dried with MgSO4, and the solvent removed on the rotary evaporator to leave a white crystalline solid. This solid is purified by column chromatography on flash grade silica gel using a 1:1 mixture of CH 2 Cl2 /Hexane as eluent. Further purification is accomplished by recrystallization of the white solid from ethanol to give white, diamond-shaped crystals (11.08 g, 59%), m.p. 96.5-97.5° C. All apparatus is rigorously dried flushed with nitrogen before use The reaction is performed in a 250 mL 3-necked flask equipped with a mechanical stirrer, a reflux condenser topped with a nitrogen inlet tube heated at reflux for 12 hours the aqueous layer is removed to leave an oil washed with 5% NaOH to remove any acidic species It is then washed with brine dried with MgSO4 the solvent removed on the rotary evaporator to leave a white crystalline solid This solid is purified by column chromatography on flash grade silica gel using a 1:1 mixture of CH 2 Cl2 /Hexane as eluent Further purification is accomplished by recrystallization of the white solid from ethanol to give white

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added bisphenol A (50 g, 219 mmol), bis(4-chlorophenyl) sulfone (22.0 g, 76.7 mmol), sodium hydroxide (20.0 g, 500 mmol), toluene (50 mL), and dimethylsulfoxide (DMSO) (250 mL). Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content. The resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene. The mixture was refluxed at 145-155° C. under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap. The toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate. The mixture was cooled to 50° C. At this time, 4-nitrophthalonitrile (50.6 g, 292 mmol) was added in one portion and the reaction mixture was heated at 80° C. for 6-8 h. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid. The material was broken up and collected using a Büchner funnel. The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution, and finally with 200 mL portions of water until neutral. The isolated solid was vacuum dried to yield the 2:1 oligomeric phthalonitrile and the bisphenol A phthalonitrile composition (100 g, 98% yield). To a 500 mL, three-necked flask fitted with a thermometer the refluxing azeotropic removal of water The resulting mixture was degassed with nitrogen at ambient temperature the Dean-Stark trap was filled with toluene was observed being collected in the Dean-Stark trap The toluene was then slowly distilled off The mixture was cooled to 50° C the reaction mixture was heated at 80° C. for 6-8 h to cool to ambient temperature resulting in the formation of a solid collected The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution dried

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added bisphenol A (50 g, 219 mmol), bis(4-chlorophenyl) sulfone (22.0 g, 76.7 mmol), sodium hydroxide (20.0 g, 500 mmol), toluene (50 mL), and dimethylsulfoxide (DMSO) (250 mL). Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content. The resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene. The mixture was refluxed at 145-155° C. under a nitrogen atmosphere for 8-16 h or until no more water was observed being collected in the Dean-Stark trap. The toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate. The mixture was cooled to 50° C. At this time, 4-nitrophthalonitrile (50.6 g, 292 mmol) was added in one portion and the reaction mixture was heated at 80° C. for 6-8 h. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid. The material was broken up and collected using a Büchner funnel. The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution, and finally with 200 mL portions of water until neutral. The isolated solid was vacuum dried to yield the 2:1 oligomeric phthalonitrile and the bisphenol A phthalonitrile composition (100 g, 98% yield). To a 500 mL, three-necked flask fitted with a thermometer the refluxing azeotropic removal of water The resulting mixture was degassed with nitrogen at ambient temperature the Dean-Stark trap was filled with toluene was observed being collected in the Dean-Stark trap The toluene was then slowly distilled off The mixture was cooled to 50° C the reaction mixture was heated at 80° C. for 6-8 h to cool to ambient temperature resulting in the formation of a solid collected The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 250 mL flask equipped with stirrer, condenser, under nitrogen atmosphere, was added 20 g (0.070 mol) of 4,4'-dichlorodiphenylsulfone, 12.8 g (0.104 mol) of 3-methyl-4-aminophenol, 15.5 g (0.112 mol) of potassium carbonate, and 130 mL of dimethylformamide. The resulting mixture was stirred at room temperature for 24 hours and at 125° for 28 hours. It was cooled and concentrated. The concentrated material was dissolved in 400 mL of toluene and washed with 4% sodium hydroxide, followed by water and brine washes. The organic layer was dried over sodium sulfate, concentrated, and chromatographed through 350 g of florisil column. Elution with hexane/ethylacetate (8/2) afforded 11.2 g (0.030 mol) of a yellow solid; mp 200° D. To a 250 mL flask equipped with stirrer, condenser, under nitrogen atmosphere It was cooled concentrated The concentrated material was dissolved in 400 mL of toluene washed with 4% sodium hydroxide The organic layer was dried over sodium sulfate concentrated chromatographed through 350 g of florisil column Elution with hexane/ethylacetate (8/2)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 112 g (1 mole) of chlorobenzene was added 123 g (1.1 moles) of chlorosulfonic acid at 10° to 20° C. After the addition, while being maintained at 20° to 30° C., the mixture was stirred for 3 hours to complete the reaction. A 0.1 mole quantity of the unreacted chlorobenzene was recovered in the same manner as in Example 1 and 32 g of 4,4'-dichlorodiphenylsulfone was obtained in 25% yield. M.P. 148.5° to 149.5° C. Purity of 99.8%. After the addition while being maintained at 20° to 30° C. the reaction A 0.1 mole quantity of the unreacted chlorobenzene was recovered in the same manner as in Example 1

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 112 g (1 mole) of chlorobenzene was added 123 g (1.1 moles) of chlorosulfonic acid at 10° to 20° C. After the addition, while being maintained at 20° to 30° C., the mixture was stirred for 3 hours to complete the reaction. A 0.1 mole quantity of the unreacted chlorobenzene was recovered in the same manner as in Example 1 and 32 g of 4,4'-dichlorodiphenylsulfone was obtained in 25% yield. M.P. 148.5° to 149.5° C. Purity of 99.8%. After the addition while being maintained at 20° to 30° C. the reaction A 0.1 mole quantity of the unreacted chlorobenzene was recovered in the same manner as in Example 1

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 211 g (1.1 moles) quantity of 4-chlorobenzenesulfonic acid was added to 112 g (1 mole) of chlorobenzene and the mixture was cooled with water while 123 g (1.1 moles) of chlorosulfonic acid was added to the mixture at about 10° to about 20° C. over a period of 1 hour. After the addition, the reaction mixture was stirred for 3 hours while being maintained at 20° to 30° C. The hydrochloric acid gas evolved during the reaction was continuously removed from the reaction system. After the termination of the reaction, about 400 ml of water was added to the reaction mixture and 11.2 g (0.1 mole) of the unreacted chlorobenzene was recovered by distillation. The separation of the precipitate formed gave 77 g of 4,4'-dichlorodiphenylsulfone in a yield of 60% (based on the amount of the aromatic hydrocarbon as consumed, the same hereinafter). M.P. 148.5° to 149.5° C. Purity of 99.8% (according to liquid chromatography, the same hereinafter). was added to the mixture at about 10° to about 20° C. over a period of 1 hour After the addition while being maintained at 20° to 30° C was continuously removed from the reaction system After the termination of the reaction, about 400 ml of water was recovered by distillation The separation of the precipitate formed

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This mixture was stirred and heated under a nitrogen atmosphere. To it was added over 8 minutes at 40°-49° C. aqueous sodium hydroxide (49.47%, 36.31 g, 447.8 mmole); the contents of the addition funnel were rinsed in with a total of about 6 ml of hot deionized water. Temperature was raised over 29 minutes to 109° C. and then over 1.5 hours to 122° C. while water was periodically drained from the Dean-Stark trap. Toluene was then removed over 27 minutes, the temperature rising to 160° C. A hot solution of 4,4'-dichlorodiphenylsulfone (64.62 g, 225.0 mmole) in toluene (75 ml) was then added over 25 minutes at a reactor temperature of 160° C., and the addition funnel was rinsed with about 10 ml of hot toluene. The mixture was stirred for 4 hours at 160°-162° C., becoming very viscous. To it were added in quick succession aqueous sodium hydroxide (49.47%, 0.19 g, 2.3 mmole), hot deionized water (about 1 ml), and toluene (5 ml). The added water was readily removed by distillation. The mixture was stirred about one hour longer at 160° C., then allowed to cool overnight. On the second day, chlorobenzene (195 g) was added, and the temperature was raised to 130° C. to effect complete solution. Methyl chloride was sparged in for one hour at 111°-114° C. to endcap the polymer; then oxalic acid 1.0 g (11 mmole) was added, and the mixture was stirred for 30 minutes at 109°-111° C. The solution was filtered through a layer of filter aid on a coarse porosity fritted-glass funnel. The polymer was recovered by coagulation in a Waring blender, washed thoroughly with water and methanol, and dried in a vacuum oven at about 150° C. Yield 66.98 g (63.4%), reduced viscosity (lg/dl in N-methylpyrrolidone at 25° C.) 0.53 dl/g. The composition of the diphenol mixture used to make this copolymer was 70 mole percent tetramethylbisphenol A/30 mole percent bisphenol. Test results on the polymer containing tetramethylbisphenol A are given in Table 6. heated under a nitrogen atmosphere the contents of the addition funnel were rinsed in with a total of about 6 ml of hot deionized water Temperature was raised over 29 minutes to 109° C. Toluene was then removed over 27 minutes rising to 160° C the addition funnel was rinsed with about 10 ml of hot toluene The mixture was stirred for 4 hours at 160°-162° C. The added water was readily removed by distillation The mixture was stirred about one hour longer at 160° C. to cool overnight On the second day, chlorobenzene (195 g) was added Methyl chloride was sparged in for one hour at 111°-114° C. the mixture was stirred for 30 minutes at 109°-111° C The solution was filtered through a layer of filter aid on a coarse porosity fritted-glass funnel The polymer was recovered by coagulation in a Waring blender washed thoroughly with water and methanol dried in a vacuum oven at about 150° C Yield 66.98 g (63.4%), reduced viscosity (lg/dl in N-methylpyrrolidone at 25° C.) 0.53 dl/g Test results on the polymer

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: passing the recovered unreacted p-chlorobenzene sulfonic acid into a reaction zone while passing monochlorobenzene countercurrent to the p-chlorobenzene sulfonic acid thereby forming additional 4,4'-dichlorodiphenyl sulfone.