Methods of manufacture of 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines, and polymers derived therefrom

1. A method for the manufacture of a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I)

the method comprising heating a reaction mixture comprising a phenolphthalein compound of formula (II)

and a primary arylamine of formula (III)

in the presence of

an acid catalyst, and

a heterocyclic aromatic amine co-catalyst,

to form the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I), wherein in formulas (I), (II), and (III),

each occurrence of R 1 is independently a C 1-25 hydrocarbyl,

each occurrence of R 2 and R 3 is independently a C 1-25 hydrocarbyl or halogen, and

r, p, and q are each independently 0 to 4.

2. The method of claim 1 , wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises 500 to 8000 parts per million of an aminophenol.

3. The method of claim 1 , wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises zero to 1000 parts per million of the phenolphthalein compound of formula (II).

4. The method of claim 1 , wherein the primary arylamine is aniline.

5. The method of claim 1 , wherein the heterocyclic aromatic amine co-catalyst has 5 to 10 atoms in the ring, and is unsubstituted or substituted with a halogen, nitro, cyano, C 1-6 alkyl, C 3-6 cycloalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkoxycarbonyl, C 6-10 aryl, C 6-10 aryloxy, C 7-10 alkylarylene, C 7-10 arylalkylene, —NR′ 2 wherein each R′ is the same or different and is a hydrogen, C 1-6 alkyl, C 6-10 aryl, C 7-10 alkylarylene, or C 7-10 arylalkylene, or two adjacent carbon atoms are substituted with a divalent moiety having from 3 to 4 atoms to form a fused aromatic ring wherein 1 or 2 of the atoms can be a nitrogen, or a combination comprising at least one of the foregoing substituents.

6. The method of claim 1 , wherein the acid catalyst is a mineral acid.

7. The method of claim 1 , wherein the heterocyclic aromatic amine co-catalyst is present at a concentration of 0.005-0.5 molar equivalents of the phenolphthalein compound of formula (II).

8. The method of claim 1 , wherein the acid catalyst is present at a concentration of 0.5-1.5 molar equivalents of the phenolphthalein compound of formula (II).

9. The method of claim 1 , wherein the primary arylamine is present at a concentration of 3.0-5.0 molar equivalents of the phenolphthalein compound of formula (II).

10. The method of claim 1 , wherein the heating is from 135 to 180° C.

11. The method of claim 1 , wherein the heating is for 8 to 40 hours.

12. The method of claim 1 , wherein the heating is for 10 to 40 hours at 135 to 150° C., and provides the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) having an aminophenol content of 400 to 1400 parts per million.

13. The method of claim 1 , further comprising

adding the acid catalyst and the primary arylamine to a solvent to form an initial composition;

removing water from the initial composition to provide a reduced water composition; and

adding the phenolphthalein compound of formula (II) and the heterocyclic aromatic amine co-catalyst to the reduced water composition to provide the reaction mixture.

14. The method of claim 1 , further comprising precipitating the phthalimidine of formula (I) from the reaction mixture to provide a crude 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

15. The method of claim 14 , further comprising purifying the crude 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

16. The method of claim 1 , wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) is of formula (IA)

wherein R 1 is a hydrogen or a C 1-3 alkyl, R 2 is a C 1-3 alkyl or a halogen, p is 0 or 1, and r is 0 or 1;

the phenolphthalein compound of formula (II) is phenolphthalein;

the heterocyclic aromatic amine co-catalyst is unsubstituted pyridine, unsubstituted imidazole, or a 4-dimethyl-aminopyridine;

the acid catalyst is a mineral acid; and

the primary arylamine of formula (III) is aniline.

17. The method of claim 1 , wherein the acid catalyst is hydrochloric acid, the primary arylamine of formula (III) is aniline, the phenolphthalein compound of formula (II) is phenolphthalein, and the heterocyclic aromatic amine co-catalyst is pyridine.

18. The method of claim 1 , wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) is of formula (IV):

the phenolphthalein compound of formula (II) is phenolphthalein;

the primary arylamine of formula (III) is aniline;

the acid catalyst is hydrochloric acid; and

the heterocyclic aromatic amine co-catalyst is pyridine.

19. A 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition, comprising

a phthalimidine of formula (I)

wherein

each occurrence of R 1 is independently a C 1-25 hydrocarbyl,

each occurrence of R 2 and R 3 is independently a C 1-25 hydrocarbyl or halogen, and

r, p, and q are each independently 0 to 4;

500 to 1200 parts per million of an aminophenol; and

zero to 1000 parts per million of a phenolphthalein compound of formula (II)

an acid catalyst and

a heterocyclic aromatic amine co-catalyst,

wherein the phthalimidine is manufactured in the presence of the acid catalyst and the heterocyclic aromatic amine co-catalyst.

20. A method for the manufacture of a polycarbonate, comprising

manufacturing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in accordance with the method of claim 1 ; and

polymerizing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in the presence of a carbonate source.

21. The composition of claim 19 , wherein the phthalimidine of formula (I) is an as-synthesized phthalimidine comprising 500 to 1000 parts per million of an aminophenol.