Methods for preparing cycloalkylidene bisphenols
View Patent ↗A process for forming a cycloalkylidene bisphenol comprises: reacting a cycloalkanone compound of formula: where [A] is a substituted or an unsubstituted aromatic group, R 1 –R 4 independently represent a hydrogen or a C 1 –C 12 hydrocarbyl group; and “a” and “b” are integers independently having values from 0–3; with an aromatic hydroxy compound of formula [A]-OH, where [A] is as previously described; at a mole ratio of greater than or equal to about 20, in the presence of a sulfonic acid type ion exchange resin catalyst crosslinked with greater than or equal to about 8 weight percent of divinylbenzene, and a promoter selected from the group consisting of a mercaptan compound and a resorcinol compound; to form a cycloalkylidene bisphenol of formula: where [A], R 1 –R 4 , “a” and “b” are as previously described. Moreover, any acid catalyst can be used with a resorcinol promoter.
1. A continuous process for forming a cycloalkylidene bisphenol, comprising:
reacting an aromatic hydroxy compound and a cycloalkanone compound in the presence of a sulfonic acid type ion exchange resin catalyst and a promoter; wherein said cycloalkanone compound is selected from the group consisting of substituted and unsubstituted tricyclo[5.2.1.0 2,6 ]decanones, and 4-perhydrocumyl cyclohexanone, wherein a mole ratio of said aromatic hydroxy compound to said cycloalkanone is greater than or equal to about 20; wherein said sulfonic acid type ion exchange resin catalyst is crosslinked with greater than or equal to about 8 weight percent of divinylbenzene relative to an overall weight of said sulfonic acid type ion exchange resin catalyst, and has a catalytic activity after at least 100 hours of run time that is greater than or equal to about 70 percent of an initial catalytic activity that was measured after about 16 hours of run time; and wherein said promoter is selected from the group consisting of a mercaptan compound and a resorcinol compound; and
forming the cycloalkylidene bisphenol having the formula:
wherein [A] is a substituted or an unsubstituted aromatic group, R 1 –R 4 independently represent a hydrogen or a C 1 –C 12 hydrocarbyl group; and “a” and “b” are integers independently having values from 0 to 3.
2. The process of claim 1 , wherein said sulfonic acid type ion exchange resin catalyst is crosslinked with about 20 weight percent of divinylbenzene relative to the overall weight of said sulfonic acid type ion exchange resin catalyst.
3. The process of claim 1 , wherein said mercaptan compound is selected from the group consisting of 3-mercaptopropionic acid, a substituted or an unsubstituted benzyl mercaptan, 3-mercapto-1-propanol, ethyl 3-mercaptopropionate, 1,4-bis(mercaptomethyl)benzene, alkanethiols of the formula R-SH, wherein “R” is a C 1 to C 10 hydrocarbyl group; and mixtures of the foregoing mercaptan compounds.
4. The process of claim 1 , wherein said resorcinol compound is of the formula:
wherein R 5 is selected from the group consisting of hydrogen, chlorine, fluorine, bromine, and C 1 –C 10 alkyl groups; and R 6 is selected from the group consisting of C 1 –C 10 alkyl groups.
5. The process of claim 1 , wherein said resorcinol compound is selected from the group consisting of resorcinol, 2-methylresorcinol, resorcinol diethyl ether, resorcinol dimethylether, 4-hexylresorcinol, 4-chlororesorcinol, and any combinations of the foregoing resorcinol compounds.
6. The process of claim 1 , wherein reacting the aromatic hydroxy compound and the cycloalkanone compound in the presence of the sulfonic acid type ion exchange resin catalyst and the promoter comprises passing the aromatic hydroxy compound and the cycloalkanone compound through the packed bed comprising said sulfonic acid type ion exchange resin catalyst at a weight hourly space velocity from about 0.25 to about 4.
7. The process of claim 1 , wherein said aromatic hydroxy compound is selected from the group consisting of phenol; ortho-cresol, meta-cresol, para-cresol, 2,6-xylenol, and mixtures of the foregoing aromatic hydroxy compounds.
8. The process of claim 1 , wherein said reacting the aromatic hydroxy compound and the cycloalkanone compound in the presence of the sulfonic acid type ion exchange resin catalyst and the promoter is in a batch, a semi-batch, or a continuous mode.
9. A method of making a polycarbonate which comprises reacting a carbonic acid derivative with a cycloalkylidene bisphenol, said cycloalkylidene bisphenol being prepared by a continuous method comprising:
reacting an aromatic hydroxy compound and a cycloalkanone compound in the presence of a sulfonic acid type ion exchange resin catalyst and a promoter, wherein said cycloalkanone compound is selected from the group consisting of substituted and unsubstituted tricyclo[5.2.1.0 2,6 ]decanones, and 4-perhydrocumyl cyclohexanone wherein a mole ratio of said aromatic hydroxy compound to said cycloalkanone is greater than or equal to about 20, wherein said sulfonic acid type ion exchange resin catalyst is crosslinked with greater than or equal to about 8 weight percent of divinylbenzene relative to an overall weight of said sulfonic acid type ion exchange resin catalyst and has a catalytic activity that is greater than or equal to about 70 percent of an initial catalytic activity which was measured after about 16 hours of run time, and wherein said promoter is selected from the group consisting of a mercaptan compound and a resorcinol compound; and
forming the cycloalkylidene bisphenol having the formula:
wherein [A] is a substituted or an unsubstituted aromatic group, R 1 –R 4 independently represent a hydrogen or a C 1 –C 12 hydrocarbyl group; and “a” and “b” are integers independently having values from 0 to 3.
10. A method for preparing a cycloalkylidene bisphenol, comprising:
reacting a mixture comprising an aromatic hydroxy compound and a cycloalkanone compound in the presence of an acid catalyst and a resorcinol compound, wherein said cycloalkanone compound is selected from the group consisting of substituted and unsubstituted tricyclo[5.2.1.0 2,6 ]decanones, and 4-perhydrocumyl cyclohexanone wherein a mole ratio of said aromatic hydroxy compound to said cycloalkanone is greater than or equal to about 20, said acid catalyst being selected from the group consisting of a sulfonic acid type ion exchange resin catalyst which is crosslinked with greater than or equal to about 8 weight percent of divinylbenzene relative to an overall weight of said sulfonic acid type ion exchange resin catalyst; and an organic sulfonic acid; and
forming said cycloalkylidene bisphenol of the formula:
wherein [A] is a substituted or an unsubstituted aromatic group, R 1 –R 4 independently represent a hydrogen or a C 1 –C 12 hydrocarbyl group; and “a” and “b” are integers independently having values from 0 to 3.
11. The method of claim 10 , wherein said cycloalkanone is selected from the group consisting of substituted and unsubstituted tricyclo decanones, and substituted and unsubstituted cyclohexanones.
12. The method of claim 10 , wherein said organic sulfonic acid is selected from the group consisting of para-toluenesulfonic acid, naphthalenesulfonic acid, methamesulfonic acid, and dodecylbenzenesulfonic acid.
13. The method of claim 10 , wherein said resorcinol compound is selected from the group consisting of resorcinol, 2-methylresorcinol, resorcinol diethyl ether, resorcinol dimethylether, 4-hexylresorcinol, 4-chlororesorcinol, and any combinations of the foregoing resorcinol compounds.
14. The method of claim 10 , further comprising adding a mercaptan compound to the mixture.
15. The method of claim 14 , wherein said mercaptan compound is selected from the group consisting of 3-mercaptopropionic acid, a substituted or an unsubstituted benzyl mercaptan, 3-mercapto-1-propanol, ethyl 3-mercaptopropionate, 1,4-bis(mercaptomethyl)benzene, alkanethiols of the formula R-SH, wherein “SR” is a C 1 to C 10 hydrocarbyl group, and mixtures of the foregoing mercaptan compounds.
16. The method of claim 10 , wherein said aromatic hydroxy compound is selected from the group consisting of phenol, ortho resol, meta-cresol, para-cresol, 2,6-xylenol, and mixtures of the foregoing aromatic hydroxy compounds.
17. The method of claim 10 , wherein said reacting the aromatic hydroxy compound and the cycloalkanone compound in the presence of the sulfonic acid type ion exchange resin catalyst and the promoter is in a batch or a continuous mode.
18. A method for producing 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, said method comprising:
reacting a mixture comprising ortho-cresol and cyclohexanone in the presence of from 10 to 15 weight percent of dodecylbenzenesulfonic acid, relative to a combined weight of ortho-cresol and cyclohexanone; and from 5000 to 15000 parts of resorcinol per million parts of the combined weights of cyclohexanone and ortho-cresol to form 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane.
19. The method of claim 18 , wherein said reacting further comprises maintaining a reaction temperature from about 50° C. to about 60° C.
20. The method of claim 18 , wherein said reacting comprises a ortho-cresol to cyclohexanone mole ratio of from about 10 to about 40.
21. The method of claim 18 , wherein said reacting comprises a reaction time of about 7 hours to about 36 hours.