Bisphenol compounds and methods of making
View Patent ↗Disclosed are bisphenol compounds, such as tetramethylcyclobutane diol-bisphenol, and processes for making and using them.
1. A compound of Formula I
wherein m and p may be the same or different and are each an integer from 0-4; each R 1 and R 2 are the same or different and are each independently selected from one or more of halogen, C 1 -C 12 alkyl, C 1 -C 6 aliphatic, C 3 -C 6 cycloaliphatic, C 1 -C 12 alkoxy, and C 1 -C 12 alkyl ester; and
R 3 , R 4 , R 5 , and R 6 are the same or different and are each independently selected from one or more of hydrogen, and C 1 -C 2 aliphatic.
2. The compound of claim 1 , wherein m is 1.
3. The compound of claim 1 , wherein p is 1.
4. The compound of claim 1 wherein m and p are 0.
5. The compound of claim 1 , wherein R 3 , R 4 , R 5 , and R 6 are each methyl.
6. A compound of Formula Ia
7. A process for preparing a compound of Formula I
comprising reacting a compound of Formula II
with a compound of Formula III
wherein m and p may be the same or different and are each an integer from 0-4;
each R 1 and R 2 are the same or different and are each independently selected from one or more of halogen, C 1 -C 12 alkyl, C 1 -C 6 aliphatic, C 3 -C 6 cycloaliphatic, C 1 -C 12 alkoxy, and C 1 -C 12 alkyl ester;
R 3 , R 4 , R 5 , and R 6 are the same or different and are each independently selected from one or more of hydrogen, and C 1 -C 2 aliphatic; and
each R 7 is independently selected from hydrogen, C 1 -C 8 aliphatic, or an aromatic.
8. The process of claim 7 , wherein the process is a solution process.
9. The process of claim 7 , wherein the process is a melt transesterification process.
10. The process of claim 7 , wherein the compound of Formula II is tetramethylcyclobutane diol.
11. The process of claim 7 , wherein the compound of Formula III is methyl 4-hydroxybenzoate.
12. The process of claim 7 , comprising:
(a) adding the compound of Formula III to a solution of the compound of Formula II, and
(b) adding a catalyst.
13. The process of claim 12 , wherein the solvent comprises xylene.
14. The process of claim 12 , wherein the catalyst is dibutyltin oxide.
15. The process of claim 12 , further comprising distilling out one or more of solvent, solvent-water azeotrope, solvent-alcohol and alcohol formed during the reaction.
16. The process of claim 7 , further comprising precipitating out the compound of Formula I.
17. The process of claim 16 , wherein precipitating out comprising cooling the reaction mixture and adding 1,2-dichloroethane.
18. The process of claim 16 , further comprising filtering the precipitated compound of Formula I, washing with hot dichloroethane, and drying.
19. The process of claim 16 , wherein the filtered precipitated solid comprises a compound of Formula I having a purity of at least about 97%.
20. A process for preparing a tetramethylcyclobutane diol-2,5-bis(4-hydroxybenzoate) of the Formula Ia
comprising:
(a) adding methyl 4-hydroxybenzoate to a solution of tetramethylcyclobutane diol,
(b) adding a catalyst,
(c) distilling out solvent and methanol formed during the reaction, and
(d) precipitating out the compound of Formula I.
21. The process of claim 20 , wherein the solvent comprises xylene.
22. The process of claim 20 , wherein the catalyst is dibutyltin oxide.
23. The process of claim 20 , wherein the solvent comprises xylene and the catalyst is dibutyltin oxide.
24. A process of purifying a mixture of a compound of Formula I.
25. The process of claim 24 , comprising:
(a) dissolving a crude mixture in a suitable solvent;
(b) adding activated carbon to the mixture and heating;
(c) filtering and washing the mixture with hot solvent; and
(d) crystallizing the mixture.
26. The process of claim 25 , comprising
(a) cooling the crystallized mixture; and
(b) precipitating the solid by filtering, washing with solvent and drying.
27. The process of claim 26 , wherein the precipitated solid comprises a compound of Formula I having a purity of at least about 99.3% after purification.
28. An article of manufacture comprising a polymer prepared from a composition containing the compound of claim 1 .
29. The article of claim 28 wherein said article is an electronic device.
30. An article of manufacture comprising a polymer prepared from a composition containing the compound of claim 6 .
31. The article of claim 30 wherein said article is an electronic device.
32. The article of claim 28 , wherein said polymer is a polycarbonate.
33. A process for preparing a tetramethylcyclobutane diol-2,5-bis(4-hydroxybenzoate) of the Formula Ia
comprising:
(a) adding methyl 4-hydroxybenzoate to a solution of tetramethylcyclobutane diol,
(b) adding a catalyst,
(c) distilling out solvent and methanol formed during the reaction,
(d) measuring the % areas of the monoester and diester in the reaction until the % area of diester is between 50% and 80% based on the areas of the monoester and diester being 100% as measured using high pressure liquid chromatography
(e) precipitating out the compound of Formula I.