Method of preparing ester-substituted diaryl carbonates
View Patent ↗The present invention relates to an interfacial method of preparing ester-substituted diaryl carbonates. The method includes the steps of: forming a reaction mixture comprising phosgene, an ester-substituted phenol, an organic solvent, and a catalyst selected from the group consisting of a tertiary amine catalyst and a phase transfer catalyst, said reaction mixture having an organic phase and an aqueous phase, wherein said aqueous phase has a brine strength; allowing the reaction mixture to react wherein during the reaction, (i) the aqueous phase has a pH, and the pH is adjusted, if necessary, by the addition of an alkali metal hydroxide solution in amounts such that the pH is greater than or equal to 9.0 during at least some portion of the reaction, and (ii) the brine strength of the aqueous phase is adjusted, if necessary, by varying the concentration of the alkali metal hydroxide solution being added to maintain the pH such that the brine strength is between 15% and a saturated brine solution during at least some portion of the reaction: thereby forming an ester-substituted diaryl carbonate, wherein the reaction mixture is formed with less than 15% water of formulation, and wherein the brine strength is maintained at or above 15% and the pH is maintained at or above 9 for a sufficient portion of the process that the ester-substituted diaryl carbonate is formed with a conversion of at least 90% and a selectivity of at least 98%.
1. A method for preparing an ester-substituted diaryl carbonate comprising the steps of:
(a) forming a reaction mixture comprising phosgene, an ester-substituted phenol, an organic solvent, and a catalyst selected from the group consisting of a tertiary amine catalyst and a phase transfer catalyst, said reaction mixture having an organic phase and an aqueous phase, wherein said aqueous phase has a brine strength,
(b) allowing the reaction mixture to react wherein during the reaction,
(i) the aqueous phase has a pH, and the pH is adjusted, if necessary, by the addition of an alkali metal hydroxide solution in amounts such that the pH is greater than or equal to 9.0 during at least some portion of the reaction, and
(ii) the brine strength of the aqueous phase is adjusted, if necessary, by varying the concentration of the alkali metal hydroxide solution being added to maintain the pH such that the brine strength is between 15% and a saturated brine solution during at least some portion of the reaction,
thereby forming an ester-substituted diaryl carbonate,
wherein the reaction mixture is formed with less than 15% water of formulation, and wherein the brine strength is maintained at or above 15% and the pH is maintained at or above 9 for a sufficient portion of the process that the ester-substituted diaryl carbonate is formed with a conversion of at least 90% and a selectivity of at least 98%.
2. The method of claim 1 , wherein the catalyst selected is a tertiary amine and the tertiary amine catalyst and the ester-substituted phenol are introduced to the reaction mixture in a mole ratio of between 0.01-0.09.
3. The method of claim 1 , wherein the ester-substituted phenol and the phosgene are introduced to the reaction mixture in a mole ratio of between 0.50 to 1.00 and 0.75 to 1.00 moles of phosgene to moles of ester-substituted phenol.
4. The method of claim 1 , wherein during the reaction of the reaction mixture the brine strength is in a range between 20% and 25% for at least a portion of the reaction.
5. The method of claim 1 , wherein the portion of the reaction during which the brine strength is greater than 15% and the pH is greater than 9 is sufficient to achieve a conversion greater than 98%.
6. The method of claim 1 , wherein during the reaction of the reaction mixture, the phosgene and ester-substituted phenol are contacted for a length of time sufficient to convert between 10% and 100% of the ester-substituted phenol to ester-substituted diaryl carbonate.
7. The method of claim 1 , wherein the ester-substituted diaryl carbonate has the structure,
wherein R 1 is independently at each occurrence a C 1 -C 20 alkyl radical, C 4 -C 20 cycloalkyl radical, or C 4 -C 20 aromatic radical; R 2 is independently at each occurrence a halogen atom, cyano group, nitro group, C 1 -C 20 alkyl radical, C 4 -C 20 cycloalkyl radical, C 4 -C 20 aromatic radical, C 1 -C 20 alkoxy radical, C 4 -C 20 cycloalkoxy radical, C 4 -C 20 aryloxy radical, C 1 -C 20 alkylthio radical, C 4 -C 20 cycloalkylthio radical, C 4 -C 20 arylthio radical, C 1 -C 20 alkylsulfinyl radical, C 4 -C 20 cycloalkylsulfinyl radical, C 4 -C 20 arylsulfinyl radical, C 1 -C 20 alkylsulfonyl radical, C 4 -C 20 cycloalkylsulfonyl radical, C 4 -C 20 arylsulfonyl radical, C 1 -C 20 alkoxycarbonyl radical, C 4 -C 20 cycloalkoxycarbonyl radical, C 4 -C 20 aryloxycarbonyl radical, C 2 -C 60 alkylamino radical, C 6 -C 60 cycloalkylamino radical, C 5 -C 60 arylamino radical, C 1 -C 40 alkylaminocarbonyl radical, C 4 -C 40 cycloalkylaminocarbonyl radical, C 4 -C 40 arylaminocarbonyl radical, or C 1 -C 20 acylamino radical; and b is independently at each occurrence an integer 0-4.
8. The method of claim 7 , wherein the ester-substituted diaryl carbonate is bis-methylsalicyl carbonate.
9. The method of claim 1 , wherein ester-substituted phenol has structure,
wherein R 1 is C 1 -C 20 alkyl radical, C 4 -C 20 cycloalkyl radical or C 4 -C 20 aromatic radical, R 2 is independently at each occurrence a hydrogen atom, halogen atom, cyano group, nitro group, C 1 -C 20 alkyl radical, C 4 -C 20 cycloalkyl radical, C 4 -C 20 aromatic radical, C 1 -C 20 alkoxy radical, C 4 -C 20 cycloalkoxy radical, C 4 -C 20 aryloxy radical, C 1 -C 20 alkylthio radical, C 4 -C 20 cycloalkylthio radical, C 4 -C 20 arylthio radical, C 1 -C 20 alkylsulfinyl radical, C 4 -C 20 cycloalkylsulfinyl radical, C 4 -C 20 arylsulfinyl radical, C 1 -C 20 alkylsulfonyl radical, C 4 -C 20 cycloalkylsulfonyl radical, C 4 -C 20 arylsulfonyl radical, C 1 -C 20 alkoxycarbonyl radical, C 4 -C 20 cycloalkoxycarbonyl radical, C 4 -C 20 aryloxycarbonyl radical, C 2 -C 60 alkylamino radical, C 6 -C 60 cycloalkylamino radical, C 5 -C 60 arylamino radical, C 1 -C 40 alkylaminocarbonyl radical, C 4 -C 40 cycloalkylaminocarbonyl radical, C 4 -C 40 arylaminocarbonyl radical, and C 1 -C 20 acylamino radical; and b is an integer 0-4.
10. The method of claim 9 , wherein the ester-substituted phenol is selected from the group consisting of phenyl salicylate, methyl salicylate, ethyl salicylate, isopropyl salicylate and benzyl salicylate.
11. The method of claim 1 , wherein the tertiary amine catalyst has structure,
wherein each R 7 , R 8 , and R 9 are independently a C 1 -C 18 alkyl group, a C 3 -C 18 cycloalkyl group, or R 7 , R 8 , and R 9 together form a C 4 -C 20 cycloaliphatic ring which may be substituted by one or more C 1 -C 20 alkyl, C 6 -C 20 aryl, C 5 -C 21 aralkyl, C 5 -C 20 cycloalkyl groups or a combination thereof.
12. The method of claim 11 , wherein the tertiary amine catalyst is selected from the group consisting of triethylamine, dimethylbutylamine, diispropylethylamine, tributylamine, and 1,4-diazabicyclooctane.
13. The method of claim 12 , wherein the tertiary amine catalyst is triethylamine.
14. The method of claim 1 , wherein the catalyst selected is a phase transfer catalyst and has the structure,
wherein R 3 -R 6 are independently a C 1 -C 20 alkyl radical, C 4 -C 20 cycloalkyl radical, or a C 4 -C 20 aryl radical, and X − is an organic or inorganic anion.
15. The method of claim 14 , wherein the phase transfer catalyst is selected from the group consisting of tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, methyl tributyl ammonium chloride, tetramethyl ammonium hydroxide, tetrabutyl ammonium chloride and decyl trimethyl ammonium chloride.
16. The method of claim 14 , wherein the phase transfer catalyst is methyl tributyl ammonium chloride.
17. The method of claim 1 , wherein during the reaction of the reaction mixture the pH is between 11 and 13.5 for at least a portion of the reaction.
18. The method of claim 1 , wherein the alkali metal hydroxide is sodium hydroxide.
19. The method of claim 1 , wherein the reaction mixture is formed with less than 10% water of formulation.
20. The method of claim 1 , wherein the reaction mixture is formed with less than 5% water of formulation.
21. The method of claim 1 , wherein the reaction mixture is formed with no water of formulation.