tributyl phosphate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Solutions of oligomeric bisphenol A polycarbonate in methyl salicylate were prepared as in Examples 1-5 at an equilibration temperature of about 160° C. using as a catalyst either TBPA alone (as in Examples 1-5) or a combination of TBPA with sodium hydroxide. The amount of catalyst employed was 2.5×10−4 moles TBPA per mole BPA and (when present) 2×106 moles sodium hydroxide per mole BPA. Following the equilibration reaction, the solution was transferred by means of nitrogen pressure (about 80 psi) to a gear pump which pumped the solution via an insulated pipe connected directly (hard plumbed) to the upstream edge of barrel one of a 25 millimeter diameter, 14 barrel, co-rotating intermeshing twin screw extruder having a length to diameter ratio of 56. The extruder comprised 6 vents V1-V6 located at the upstream edges of barrel four (V1, vacuum or atmospheric vent), barrel five (V2, optionally closed but at times operated as atmospheric or vacuum vent), barrel seven (V3, vacuum vent), barrel nine (V4, vacuum vent), barrel eleven (V5, vacuum vent) and barrel thirteen (V6, vacuum vent). Vent V1 was operated at atmospheric pressure or alternatively under a slight vacuum (5-10 in. Hg, as measured by a vacuum gauge). Vacuum vents V3 and V4 were operated at moderate vacuum (10-28 in. Hg). Vacuum vents V5 and V6 were operated at moderate to high (>29 in Hg) vacuum. When operated at slight to moderate vacuum (5-28 in Hg), vacuum was supplied to vents V2-V6 with “house” vacuum. In a number of instances, vacuum vent V6 or vacuum vents V5 together with V6 were operated under high (i.e. “full”) vacuum (˜29 in. Hg. as measured by a vacuum gauge). The vacuum vents were connected through solvent recovery manifold and condenser systems to their respective sources of vacuum. In instances in which either V6 alone or V5 and V6 were operated at “full” vacuum, the vent or vents being operated at “full” vacuum were connected via a cold trap to a vacuum pump. Vents V1 and V3-V6 were equipped with type “C” vent port inserts. Vent port inserts are available from the Werner & Pfleiderer Company. Vent port inserts differ in the cross sectional area available for the solvent vapors to escape the extruder: Type “A” inserts are the most restrictive (smallest cross section) and Type “C” are the east restrictive (largest cross section). As noted, V2 was kept closed in some instances and remained open in others. The screw design comprised conveying elements under the feed inlet and all vents. The screw design further comprised kneading blocks in four “reaction zones” (zones comprising screw elements providing intense mixing) located between vents. The four reaction zones were located between V2 and V3, between V3 and V4, between V4 and V5, and between V5 and V6 respectively. The data in Tables 2-5 below demonstrate the effects of changes in reaction conditions on the properties of the product polycarbonate. the equilibration reaction optionally closed but at times were connected via a cold trap to a vacuum pump Vents V1 and V3-V6 were equipped with type “C” V2 was kept closed in some instances in four “reaction zones” (zones comprising screw elements providing intense mixing) The four reaction zones

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

Procedure: In an especially contemplated arm extension strategy depicted in FIG. 4, in which AD represents an adamantane or diamantane group. Phenylacetylene is a starting molecule that is reacted (A1) with TBPA (supra) to yield 1,3,5,7-tetrakis[3′/4′-(phenylethynyl)phenyl]adamantane. Alternatively, phenylacetylene can be converted (B1) to 4-(phenylethynyl)phenylbromide that is subsequently reacted (C1) with trimethylsilylacetylene to form 4-(phenylethynyl)phenylacetylene. TBPA can then be reacted (with phenylethynylphenylacetylene to 1,3,5,7-tetrakis{3′/4′-[4″-(phenylethynyl)phenylethynyl]phenyl}-adarnantane. In a further extension reaction, phenylethynylphenylacetylene is reacted (2) with 1-bromo-4-iodobenzene to form 4-[4′-(phenylethynyl)phenylethynyl]phenylbromide that is further converted (C2) to 4-[4′-(phenylethynyl)phenylethynyl]acetylene. The so formed 4-[4′-(phenylethynyl)phenylethynyl]acetylene may then be reacted (A3) with TBA to yield 1,3,5,7-tetrakis-{3′/4′-[4″-(4′-(phenylethynyl)phenylethynyl)phenylethynyl]phenyl}adamantane.

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

Procedure: Using a reactor setup as described in Example 1, a TBPA, glycol, maleic anhydride product was prepared using a mole ratio of anhydride to glycol of 4:5.23, a hydroxybutyltin oxide catalyst and diethanolamine (DEA) as neutralizing agent. TBPA (1.937 moles), ethylene glycol (3.377 moles), diethylene glycol (1.69 moles), hydroxy-butyltin oxide (1.49 gms), and DEA (4.41 gms) were added to the reaction at room temperature and stirred at 400 rpm. When the temperature reached 85° C., 1.937 moles of maleic; anhydride were added and the temperature was raised to 185° C. to 190° C. The reaction time was about 3 hours with 62.5 mls of water collected (86.8% of theory). The product acid number was 18.8. GPC analysis as described in Example 1 gave the following results: reached 85° C. the temperature was raised to 185° C. to 190° C collected (86.8% of theory) gave the following results

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

Procedure: Using a reactor setup as described in Example 1, a TBPA, glycol, maleic anhydride product was prepared using a mole ratio of anhydride to glycol of 4:5.23, a hydroxybutyltin oxide catalyst and diethanolamine (DEA) as neutralizing agent. TBPA (1.937 moles), ethylene glycol (3.377 moles), diethylene glycol (1.69 moles), hydroxy-butyltin oxide (1.49 gms), and DEA (4.41 gms) were added to the reaction at room temperature and stirred at 400 rpm. When the temperature reached 85° C., 1.937 moles of maleic; anhydride were added and the temperature was raised to 185° C. to 190° C. The reaction time was about 3 hours with 62.5 mls of water collected (86.8% of theory). The product acid number was 18.8. GPC analysis as described in Example 1 gave the following results: reached 85° C. the temperature was raised to 185° C. to 190° C collected (86.8% of theory) gave the following results

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

Procedure: The procedure described in Example 1 was followed except that 7.57 g of a 70% solution of ammonium lactate was combined with 50 g tributyl phosphate. The reaction mixture was heated for 0.5 hour at 110–118° C. and a reduced pressure of 4.5–5.5 mm Hg, resulting in a conversion of about 97% from ammonium lactate to lactic acid. The reaction mixture was heated for 0.5 hour at 110–118° C.

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Solutions of oligomeric bisphenol A polycarbonate in methyl salicylate were prepared as in Examples 1-5 at an equilibration temperature of about 160° C. using as a catalyst either TBPA alone (as in Examples 1-5) or a combination of TBPA with sodium hydroxide. The amount of catalyst employed was 2.5×10−4 moles TBPA per mole BPA and (when present) 2×106 moles sodium hydroxide per mole BPA. Following the equilibration reaction, the solution was transferred by means of nitrogen pressure (about 80 psi) to a gear pump which pumped the solution via an insulated pipe connected directly (hard plumbed) to the upstream edge of barrel one of a 25 millimeter diameter, 14 barrel, co-rotating intermeshing twin screw extruder having a length to diameter ratio of 56. The extruder comprised 6 vents V1-V6 located at the upstream edges of barrel four (V1, vacuum or atmospheric vent), barrel five (V2, optionally closed but at times operated as atmospheric or vacuum vent), barrel seven (V3, vacuum vent), barrel nine (V4, vacuum vent), barrel eleven (V5, vacuum vent) and barrel thirteen (V6, vacuum vent). Vent V1 was operated at atmospheric pressure or alternatively under a slight vacuum (5-10 in. Hg, as measured by a vacuum gauge). Vacuum vents V3 and V4 were operated at moderate vacuum (10-28 in. Hg). Vacuum vents V5 and V6 were operated at moderate to high (>29 in Hg) vacuum. When operated at slight to moderate vacuum (5-28 in Hg), vacuum was supplied to vents V2-V6 with “house” vacuum. In a number of instances, vacuum vent V6 or vacuum vents V5 together with V6 were operated under high (i.e. “full”) vacuum (˜29 in. Hg. as measured by a vacuum gauge). The vacuum vents were connected through solvent recovery manifold and condenser systems to their respective sources of vacuum. In instances in which either V6 alone or V5 and V6 were operated at “full” vacuum, the vent or vents being operated at “full” vacuum were connected via a cold trap to a vacuum pump. Vents V1 and V3-V6 were equipped with type “C” vent port inserts. Vent port inserts are available from the Werner & Pfleiderer Company. Vent port inserts differ in the cross sectional area available for the solvent vapors to escape the extruder: Type “A” inserts are the most restrictive (smallest cross section) and Type “C” are the cast restrictive (largest cross section). As noted, V2 was kept closed in some instances and remained open in others. The screw design comprised conveying elements under the feed inlet and all vents. The screw design further comprised kneading blocks in four “reaction zones” (zones comprising screw elements providing intense mixing) located between vents. The four reaction zones were located between V2 and V3, between V3 and V4, between V4 and V5, and between V5 and V6 respectively. The data in Tables 2-5 below demonstrate the effects of changes in reaction conditions on the properties of the product polycarbonate. the equilibration reaction optionally closed but at times were connected via a cold trap to a vacuum pump Vents V1 and V3-V6 were equipped with type “C” V2 was kept closed in some instances in four “reaction zones” (zones comprising screw elements providing intense mixing) The four reaction zones

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

Procedure: The same reaction was tried in a modified cell, without the crank 23. 2 g (14 mmol) of 1-methylnaphthalene in 3 g of tributylphosphate was allowed to react for 40 hours with electrochemically produced Co(III) sulphate at 40°-45° C. The electrolyte solution was composed of 0.12M Co(II) sulphate in 2M H2SO4. The current was 200 mA. The organic material isolated from this run was placed on a silica gel column, which was eluted with a solution of 5% ether in petroleum ether (bp=60°-80° C.). The initial band consisted of 860 mg (6 mmol, 43%) of starting material. The second band yielded 447 mg (2.9 mmol) of 1-naphthaldehyde. The aldehyde yield was 36% based on consumed starting material. The aldehyde yield was 36% based on consumed starting material. The infrared spectrum of the product was identical to that of an authentic sample. The same reaction The organic material isolated from this run was eluted with a solution of 5% ether in petroleum ether (bp=60°-80° C.)

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

Procedure: Tributylphosphate (137.2 g, 0.505 mole) was added dropwise, slowly, to a 300 ml flask containing 41.5 g (99%, 0.5 mole) N-methylimidazole at 170° C. under nitrogen and stirring. The liquid was stirred at the same temperature for an additional 5 hours. The liquid was cooled and moved to a rotary evaporator and dried at 150° C./5 mm Hg for 4 hours. The product (171.3 g, yield 98%) was pure, as judged from NMR, and was liquid at room temperature. 1H-NMR (CDCl3, 300.13 MHz, δ): 10.37 (s, 1H, —N—CH═N—), 7.50 (s, 1H, —N—CH═CH—N—), 7.29)s, 1H, —N—CH═CH—N—), 4.09 (t, 2H, —N—CH2—CH2CH2CH3), 3.87 (s, 3H, —N—CH3), 3.67 (m, 4H, —O—CH2—CH2CH2CH3), 1.67 (qu, 2H, —NCH2—CH2—CH2CH3), 1.40 (m, 4H, 2×—OCH2—CH2—CH2CH3), 1.16 (m, 4H, —OCH2CH2—CH2—CH3), 1.16 (m, 2H, —NCH2CH2—CH2CH3), 0.70 (m, 6H, 2×—OCH2CH2CH2—CH3), 0.70 (m, 3H, —NCH2CH2CH2—CH3). 31P-NMR (CDCl3, 81.015 MHz, δ): 0.95 [s, (RO)2—P(═O)—O−]. The liquid was stirred at the same temperature for an additional 5 hours The liquid was cooled moved to a rotary evaporator dried at 150° C./5 mm Hg for 4 hours