Production of low color polyetherimides
View Patent ↗The production of low color polyetherimides, including its intermediates, such as bisimides and diaryl diether dianhydrides, may be affected by producing an improved purity intermediate of 4-nitro-N-alkylphthalimide. A salt, such as alkali metal carbonate or alkali metal hydrogen carbonate, is added to an aqueous mixture of 4-nitro-N-alkylphthalimide and 3-nitro-N-alkylphthalimide to selectively hydrolyze the imide linkage of 3-nitro-N-alkylphthalimide forming a water-soluble acid-amide salt. An organic solvent is added to this salt mixture to phase separate 4-nitro-N-alkylphthalimide having dissolved in the organic solvent from acid-amide salt of 3-nitro-N-alkylphthalimide having dissolved in water.
1. A process for isolating 4-nitro-N-alkylphthalimide from an aqueous mixture of 4-nitro-N-alkylphthalimide and 3-nitro-N-alkylphthalimide comprising the steps of:
(a) providing a first mixture comprising (i) solids comprising 4-nitro-N-alkylphthalimide and 3-nitro-N-alkylphthalimide and (ii) water;
(b) adding a salt selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal carbonates, hydrogen carbonates and mixtures thereof to the first mixture, thereby forming a second mixture;
(c) stirring the second mixture under conditions sufficient for selective hydrolysis of the imide linkage of 3-nitro-N-alkylphthalimide into a water-soluble acid-amide salt of 3-nitro-N-alkylphthalimide, thereby forming a third mixture;
(d) adding an organic solvent to the third mixture, thereby forming a fourth mixture comprising (i) an organic phase comprising 4-nitro-N-alkylphthalimide dissolved in the organic solvent and (ii) an aqueous phase comprising dissolved acid-amide salt of 3-nitro-N-alkylphthalimide; and
(e) separating the organic phase from the aqueous phase.
2. The process of claim 1 , wherein in step (a), the first mixture is elevated to a temperature ranging from 20 to 60° C.
3. The process of claim 1 , wherein in step (a) through step (c), the first mixture and second mixture are maintained at a temperature ranging from 20 to 60° C.
4. The process of claim 1 , wherein in step (a), the first mixture is provided comprising from 10 to 40 weight percent solids and from 90 to 60 weight percent water.
5. The process of claim 1 , wherein in step (a), the first mixture is provided comprising from 20 to 30 weight percent solids and from 80 to 70 weight percent water.
6. The process of claim 1 , wherein in step (a), the first mixture is provided further comprising proton-bearing impurities; in step (c), the proton bearing impurities are converted to water soluble alkali metal salts; and in step (d) the aqueous phase further comprises dissolved alkali metal salts of the proton-bearing impurities.
7. The process of claim 6 , wherein in step (a), the proton-bearing impurities are selected from the group consisting of residual nitric acids, sulfuric acids, nitrophthalic acids, oxalic acids, and combinations thereof.
8. The process of claim 6 , wherein in step (a), the solids comprise from 94.0 to 99.9 weight percent 4-nitro-N-alkylphthalimide, from 0.1 to 5.0 weight percent 3-nitro-N-alkylphthalimide, and from more than 0 to 1.0 weight percent proton-bearing impurities.
9. The process of claim 1 , wherein in step (b), the salt is sodium carbonate or sodium hydrogen carbonate.
10. The process of claim 1 , wherein in step (b), the salt is added in an amount ranging from 0.1 to 7 weight percent of salt, based on the total weight percent of solids in the first mixture.
11. The process of claim 1 , wherein in step (b), the salt is added in an amount ranging from 1 to 5 weight percent of salt, based on the total weight percent of solids in the first mixture.
12. The process of claim 1 , wherein in step (c), the second mixture is stirred for a period ranging from 2 to 48 hours.
13. The process of claim 1 , wherein in step (c), the second mixture is stirred for a period ranging from 2 to 8 hours.
14. The process of claim 1 , wherein in step (c), the second mixture is stirred for a period ranging from 2 to 4 hours.
15. The process of claim 1 , wherein in step (c), the third mixture has a pH ranging from 8.5 to 12.
16. The process of claim 1 , wherein in step (d), the organic solvent is selected from the group consisting of toluene, xylene, chlorobenzene benzene, and combinations thereof.
17. The process of claim 16 , wherein in step (d) the organic solvent is toluene.
18. The process of claim 6 , wherein in step (d), the organic phase comprises from more than 0 to less than 2 weight percent 3-nitro-N-alkylphthalimide and proton-bearing impurities, based on the total weight percent of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide and proton-bearing impurities.
19. The process of claim 6 , wherein in step (d), the organic phase comprises from more than 0 to less than 1 weight percent 3-nitro-N-alkylphthalimide and more than 0 to less 500 parts per million proton-bearing impurities, based on the total weight percent of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide and proton-bearing impurities.
20. The process of claim 1 , prior to step (a), further comprising the steps of nitrating N-alkylphthalimide in an acid selected from the group consisting of nitric acid and mixtures of nitric acid and sulfuric acid to form a nitration product, and washing with water the nitration product to form the first mixture.
21. The process of claim 1 , wherein in step (a), the first mixture further comprises a member selected from the group consisting of 4-substituted-nitro -N-alkylphthalimide, 3-substituted-nitro-N-alkylphthalimide, and mixtures thereof; wherein substituted substituents are selected from the group consisting of chloro substituents, bromo substituents, fluoro substituents, and combinations thereof.
22. A process for isolating 4-nitro-N-alkylphthalimide from an aqueous mixture of 4-nitro-N-alkylphthalimide, 3-nitro-N-alkylphthalimide, and proton-bearing impurities comprising the steps of:
(a) providing a first mixture comprising a water slurry comprising solids comprising 4-nitro-N-alkylphthalimide, 3-nitro-N-alkylphthalimide, and proton-bearing impurities;
(b) adding a salt selected from the group consisting of sodium carbonate and sodium hydrogen carbonate to the first mixture, thereby forming a second mixture;
(c) stirring the second mixture under conditions sufficient for selective hydrolysis of the imide linkage of 3-nitro-N-alkylphthalimide into a water-soluble acid-amide salt of 3-nitro-N-alkylphthalimide and to convert the proton-bearing impurities to water soluble alkali metal salts, thereby forming a third mixture;
(d) adding toluene to the third mixture, thereby forming a fourth mixture comprising (i) an organic phase comprising 4-nitro-N-alkylphthalimide dissolved in toluene and (ii) an aqueous phase comprising dissolved acid-amide salt of 3-nitro -N-alkylphthalimide and alkali metal salts of the proton-bearing impurities; and
(e) separating the organic phase from the aqueous phase.
23. The process of claim 22 , wherein in step (a), the first mixture is elevated to a temperature ranging from 20 to 60° C.
24. The process of claim 22 , wherein in step (a) through step (c), the first mixture and second mixture are maintained at a temperature ranging from 20 to 60° C.
25. The process of claim 22 , wherein in step (a), the proton-bearing impurities are selected from the group consisting of residual nitric acids, sulfuric acids, nitrophthalic acids, oxalic acids, and combinations thereof.
26. The process of claim 22 wherein in step (a), the solids comprise from 94.0 to 99.9 weight percent 4-nitro-N-alkylphthalimide, from 0.1 to 5.0 weight percent 3-nitro-N-alkylphthalimide, and from more than 0 to 1.0 weight percent proton-bearing impurities.
27. The process of claim 22 , wherein in step (a), the first mixture is provided comprising from 20 to 30 weight percent solids and from 80 to 70 weight percent water.
28. The process of claim 22 , wherein in step (b), the salt is added in an amount ranging from 1 to 5 weight percent of salt, based on the total weight percent of solids in the first mixture.
29. The process of claim 22 , wherein in step (c), the second mixture is stirred for a period ranging from 2 to 48 hours.
30. The process of claim 22 wherein in step (c), the third mixture has a pH ranging from 8.5 to 12.
31. The process of claim 22 , wherein in step (d), the organic phase comprises from more than 0 to less than 2 weight percent 3-nitro-N-alkylphthalimide and proton-bearing impurities, based on the total weight percent of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide and proton-bearing impurities.
32. The process of claim 22 , wherein in step (d), the organic phase comprises from more than 0 to less than 1 weight percent 3-nitro-N-alkylphthalimide and more than 0 to less 500 parts per million proton-bearing impurities, based on the total weight percent of 3-nitro-N-alkylphthalimide, 4-nitro-N-alkylphthalimide and proton-bearing impurities.