Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom
View Patent ↗Disclosed herein is a method for producing a 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine. The method comprises forming a reaction mixture comprising at least one substituted or unsubstituted phenolphthalein compound, at least one substituted or unsubstituted primary hydrocarbyl amine, and an acid catalyst; and heating the reaction mixture to form 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine. An adduct of the 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine is formed either by using an excess of the primary hydrocarbyl amine in the first heating step, or by isolating crude 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine after the heating step and then reacting with a further amount of the primary hydrocarbyl amine. The 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine has a formula: where R 1 is selected from the group consisting of a hydrogen and a hydrocarbyl group, and R 2 is selected from the group consisting of a hydrogen, a hydrocarbyl group, and a halogen.
1. A method for producing a 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine of the formula
wherein R2 is selected from the group consisting of hydrogen, a halogen, and a hydrocarbyl selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an arylalkyl group having 7 to 25 carbon atoms, wherein the method comprises:
heating a reaction mixture comprising
a phenolphthalein compound of the formula:
wherein R 2 is selected from the group consisting of hydrogen, a halogen, and a hydrocarbyl selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an arylalkyl group having 7 to 25 carbon atoms,
a primary aromatic amine of the formula R 1 -NH 2 , wherein R 1 is an aromatic group having 6 to 25 carbon atoms, and
hydrogen chloride fluid;
neutralizing the mixture with sodium bicarbonate;
precipitating an adduct of the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine and the primary aromatic amine by adding an aromatic hydrocarbon to the neutralized reaction mixture; and
heating the precipitated adduct with an alcohol to produce the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.
2. A method for producing a 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine of the formula
wherein R 2 is selected from the group consisting of hydrogen, a halogen, and a hydrocarbyl selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an arylalkyl group having 7 to 25 carbon atoms, wherein the method comprises:
heating a reaction mixture comprising
a phenolphthalein compound of the formula:
wherein R 2 is selected from the group consisting of hydrogen, a halogen, and a hydrocarbyl selected from the group consisting of an alkyl group having 1 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an arylalkyl group having 7 to 25 carbon atoms,
a primary aromatic amine of the general formula R 1 -NH 2 , where R 1 an aromatic group having 6 to 25 carbon atoms, and
hydrogen chloride fluid;
neutralizing the heated reaction mixture with sodium bicarbonate;
precipitating an adduct of the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine and the primary aromatic amine by adding an aromatic hydrocarbon to the neutralized reaction mixture;
dissolving the precipitated adduct in an aqueous alkali metal hydroxide solution to provide a first solution;
adding an aqueous acid to the first solution to precipitate the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine; and
heating the precipitated 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine with an alcohol to produce the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.
3. The method of claim 1 , wherein the heating of the reaction mixture in conducted at a temperature of 140 to 180° C.
4. The method of claim 1 , wherein the heating of the reaction mixture further comprises removing a distillate comprising water.
5. The method of claim 1 , wherein the aromatic hydrocarbon comprises a solvent selected from the group consisting of toluene, isomeric xylenes, mixtures of isomeric xylenes, chlorobenzene, and mesitylene.
6. The method of claim 1 , wherein the adduct comprises about two moles of the primary amine compound per mole of the phenolphthalein compound.
7. The method of claim 1 , wherein the alcohol is an aliphatic alcohol having 1 to 8 carbon atoms.
8. The method of claim 1 , wherein the alcohol is methanol, ethanol, or isopropanol.
9. The method of claim 1 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine has a purity of equal to or greater than 99.5 percent as determined by high performance liquid chromatography.
10. The method of claim 1 , wherein R 2 is hydrogen and the primary amine is aniline.
11. The method of claim 10 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine comprises less than or equal to 1,500 parts per million of the phenolphthalein compound, based on the total weight of 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.
12. The method of claim 10 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine has a purity of equal to or greater than 99.5 percent as determined by high performance liquid chromatography.
13. The method of claim 2 , wherein the heating of the reaction mixture is conducted at a temperature of 140 to 180° C.
14. The method of claim 2 , wherein the heating of the reaction mixture further comprises removing a distillate comprising water.
15. The method of claim 2 , wherein the aromatic hydrocarbon comprises a solvent selected from the group consisting of toluene, isomeric xylenes, chlorobenzene, and mesitylene.
16. The method of claim 2 , wherein the adduct comprises about two moles of the primary amine compound per mole of the phenolphthalein compound.
17. The method of claim 2 , wherein the alcohol is an aliphatic alcohol having 1 to 8 carbon atoms.
18. The method of claim 2 , wherein the alcohol is methanol, ethanol, or isopropanol.
19. The method of claim 2 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine has a purity of equal to or greater than 99.5 percent as determined by high performance liquid chromatography.
20. The method of claim 2 , wherein R 2 is hydrogen and the primary amine is aniline.
21. The method of claim 20 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine comprises less than or equal to 1,500 parts per million of the phenolphthalein compound, based on the total weight of 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.
22. The method of claim 20 , wherein the 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine has a purity of equal to or greater than 99.5 percent as determined by high performance liquid chromatography.
23. The method of claim 1 , wherein said 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine comprises less than or equal to about 1,500 parts per million of the phenolphthalein compound relative to the total weight of said 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.
24. The method of claim 2 , wherein said 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine comprises less than or equal to about 1,500 parts per million of the phenolphthalein compound relative to the total weight of said 2-hydrocarbyl-3,3-bis(4-hydroxyphenyl)phthalimidine.