Process for stabilizing phenolic resins containing calixarenes
View Patent ↗This invention relates to a process for stabilizing a phenolic resin containing a mixture of linear phenolic resins and calixarenes and a demulsifier composition comprising the stabilized phenolic resins prepared from the process. The process comprises contacting the phenolic resin with an alkylene carbonate, in the presence of a base catalyst, to at least partially alkoxylate the phenolic hydroxyl groups of the calixarenes. This process forms a stabilized phenolic resin with an increased solubility in a hydrocarbon solvent.
1. A stabilized phenolic resin prepared by the process comprising:
contacting, in a one-step process, a phenolic resin containing a mixture of linear phenolic resins and calixarenes, with an alkylene carbonate, in the presence of a base catalyst, to at least partially alkoxylate the phenolic hydroxyl groups of the calixarenes, thereby forming a stabilized phenolic resin mixture,
wherein about 0.2 to 1 mole of alkylene carbonate reacts with the phenolic hydroxyl groups for each mole of the phenolic resin.
2. The stabilized phenolic resin of claim 1 , wherein the phenolic hydroxyl groups of the linear phenolic resins are also at least partially alkoxylated.
3. The stabilized phenolic resin of claim 1 , wherein the alkylene carbonate is propylene carbonate, ethylene carbonate, or butylene carbonate.
4. The stabilized phenolic resin of claim 1 , wherein the benzene ring of the linear phenolic resins and calixarenes is independently substituted by H, C 1 to C 30 alkyl, phenyl, or arylalkyl.
5. The stabilized phenolic resin of claim 1 , wherein the linear phenolic resins and calixarenes independently contain a C 1 to C 7 alkyl substituent on the benzene ring.
6. The stabilized phenolic resin of claim 1 , wherein the phenolic resin contains about 20% to about 75% calixarenes.
7. The stabilized phenolic resin of claim 6 , wherein the phenolic resin contains about 20% to about 50% calixarenes.
8. The stabilized phenolic resin of claim 1 , wherein about 0.25 to 1 mole of alkylene carbonate reacts with the phenolic hydroxyl groups for each mole of the phenolic resin.
9. A stabilized phenolic resin prepared by the process comprising:
contacting, in a one-step process, a phenolic resin containing a mixture of linear phenolic resins and calixarenes, with an alkylene carbonate, in the presence of a base catalyst and a hydrocarbon solvent, to at least partially alkoxylate the phenolic hydroxyl groups of the calixarenes, thereby forming a stabilized phenolic resin mixture,
wherein less than 10% of the calixarenes precipitate out of the solvent after 24 hours.
10. The stabilized phenolic resin of claim 9 , wherein less than 5% of the calixarenes precipitate out of the solvent after 24 hours.
11. The stabilized phenolic resin of claim 9 , wherein the stabilized phenolic resin mixture is substantially free of undissolved solid components, without adding additional solvents.
12. The stabilized phenolic resin of claim 9 , wherein less than 10% of the calixarenes precipitate out of the solvent after being exposed to temperatures of −25° C. or greater for 24 hours.
13. The stabilized phenolic resin of claim 9 , wherein the process further comprises the step of reacting the stabilized phenolic resin with an alkylene oxide.
14. The stabilized phenolic resin of claim 9 , wherein the process further comprises an additional step of reacting the stabilized phenolic resin with an alkylene carbonate.
15. A hydrocarbon-soluble phenolic resin prepared by the process comprising:
contacting, in a one-step process, a phenolic resin containing a mixture of linear phenolic resins and calixarenes, with an alkylene carbonate, in the presence of a base catalyst, to at least partially alkoxylate the phenolic hydroxyl groups of the calixarenes thereby forming a hydrocarbon-soluble phenolic resin mixture,
wherein the solubility of the linear phenolic resin/calixarene mixture in a hydrocarbon solvent is increased by at least 50%.
16. The hydrocarbon-soluble phenolic resin of claim 15 , wherein the solubility of the linear phenolic resin/calixarene mixture in a hydrocarbon solvent is increased by at least 60%.
17. The hydrocarbon-soluble phenolic resin of claim 15 , wherein the solubility of the linear phenolic resin/calixarene mixture in a hydrocarbon solvent is increased by at least 120%.
18. The stabilized phenolic resin prepared by the process of claim 1 , wherein each partially alkoxylated calixarene has the structure of
wherein, R is H, C 1 to C 30 alkyl, phenyl, or arylalkyl;
n is independently 2 to 20; and
each p is independently 0 to 8 provided that at least one of the p variables is at least 1.
19. The stabilized phenolic resin of claim 18 , wherein each p is independently 0 or 1.
20. The stabilized phenolic resin of claim 18 , wherein each R is independently a C 1 to C 7 alkyl substituent.