AN ISOMERIZATION PROCESS OF PRODUCT OBTAINED FROM BISPHENOL PREPARATION FROM A CONDENSATION REACTION OF KETONE AND PHENOL

Abstract

The present invention relates to an isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol comprising contacting the product obtained from bisphenol preparation from a condensation reaction of ketone and phenol with the ion exchange resin in aqueous condition for the isomerization of the undesired product and separating the product having higher bisphenol content, wherein said ion exchange resin is aromatic polymer having the sulfonic acid group modified with at least one promoter selected from the compound shown in the structure (I):

##STR00001##

Claims

1. An isomerization process of a product obtained from a bisphenol preparation from a condensation reaction of a ketone and a phenol comprising contacting the product obtained from the bisphenol preparation from a condensation reaction of the ketone and the phenol with an ion exchange resin in aqueous condition for the isomerization of an undesired product comprising 2,4′-isopropylidenediphenol and separating a product having higher bisphenol content, wherein said ion exchange resin is an aromatic polymer having a sulfonic acid group modified with a promoter comprising: a) at least one promoter selected from the compound shown in the structure (I): ##STR00007## wherein, X represents heteroatoms; and n is an integer from 1 to 4, and b) at least one promoter of an aminoalkyl mercaptan.

2. The process according to claim 1, wherein the promoter is the compound shown in the structure (II) or compound shown in the structure (III): ##STR00008##

3. The process according to claim 1, wherein the aminoalkyl mercaptan is cysteamine.

4. (canceled)

5. The process according to claim 13, wherein the promoter comprises the aminoalkyl mercaptan in the amount of 10 to 90% by mole of total promoter.

6. The process according to claim 5, wherein the promoter comprises the aminoalkyl mercaptan in the amount of 30 to 70% by mole of total promoter.

7. The process according to claim 1, wherein the sulfonic acid group modified with promoter is 10 to 20% of total sulfonic acid group.

8. The process according to claim 1, wherein the sulfonic acid group is modified with promoter via ionic bond.

9. The process according to claim 1, wherein the aromatic polymer having sulfonic acid group is selected from polystyrene having sulfonic acid group or styrene-divinylbenzene copolymer having sulfonic acid group.

10. The process according to claim 9, wherein the aromatic polymer having sulfonic acid group is the styrene-divinylbenzene copolymer having sulfonic acid group.

11. The process according to claim 10, wherein the styrene-divinylbenzene copolymer having sulfonic acid group has divinylbenzene in the amount of 1 to 15% by weight.

12. The process according to claim 11, wherein the styrene-divinylbenzene copolymer having sulfonic acid group has divinylbenzene in the amount of 10 to 15% by weight.

13. The process according to claim 1, wherein the aromatic polymer having sulfonic acid group has particle size in the range of 500 to 1500 micron.

14. The process according to claim 13, wherein the aromatic polymer having sulfonic acid group has particle size in the range of 600 to 850 micron.

15. The process according to claim 1, wherein the weight ratio of ion exchange resin to product obtained from the bisphenol preparation is in the range of 1:1 to 1:5.

16. The process according to claim 15, wherein the weight ratio of ion exchange resin to product obtained from the bisphenol preparation is in the range of 1:1 to 1:3.

17. The process according to claim 1, wherein said isomerization reaction is performed at the temperature in the range of 40 to 120° C. and at atmospheric pressure.

18. The process according to claim 17, wherein said isomerization reaction is performed at the temperature in the range of 60 to 80° C. and at atmospheric pressure.

19. The process according to claim 1, wherein said isomerization reaction is performed in aqueous condition having water content in the range of 0.01 to 3.5% by weight.

20. The process according to claim 19, wherein said isomerization reaction is performed in aqueous condition having water content in the range of 0.05 to 0.5% by weight.

21. The process according to claim 1, wherein the product obtained from the bisphenol preparation further comprises 4,4′-isopropylidenediphenol.

Description

DESCRIPTION OF THE INVENTION

[0016] The present invention relates to the isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol using ion exchange resin comprising the aromatic polymer having the sulfonic acid group modified with the promoter.

[0017] Any aspect being described herein also means to include the application to other aspects of this invention unless stated otherwise.

Definitions

[0018] Technical terms or scientific terms used herein have definitions as understood by an ordinary person skilled in the art unless stated otherwise.

[0019] Any tools, equipment, methods, or chemicals named herein mean tools, equipment, methods, or chemicals being operated or used commonly by those person skilled in the art unless stated otherwise that they are tools, equipment, methods, or chemicals specific only in this invention.

[0020] Use of singular noun or singular pronoun with “comprising” in claims or specification means “one” and also including “one or more”, “at least one”, and “one or more than one”.

[0021] All compositions and/or methods disclosed and claims in this application are intended to cover embodiments from any operation, performance, modification, or adjustment any factors without any experiment that significantly different from this invention, and obtain with object with utility and resulted as same as the present embodiment according to person ordinary skilled in the art although without specifically stated in claims. Therefore, substitutable or similar object to the present embodiment, including any minor modification or adjustment that can be apparent to person skilled in the art should be construed as remains in spirit, scope, and concept of invention as appeared in appended claims.

[0022] Throughout this application, term “about” means any number that appeared or expressed herein that could be varied or deviated from any error of equipment, method, or personal using said equipment or method, including variations or deviations occurred from changes in reaction conditions of uncontrollable factors such as humidity and temperature.

[0023] Heteroatom means to include the atom of the non-carbon element and said atom includes but not limited to tetrels group elements which are silicon, germanium, tin, and lead; pniktogens group elements which are nitrogen, phosphorus, arsenic, antimony, and bismuth; chalcogens group elements which are oxygen, sulfur, selenium, and tellurium; or halogens group elements which are fluorine, chlorine, bromine, and iodine.

[0024] Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

[0025] The present invention relates to the isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol comprising contacting the product obtained from bisphenol preparation from a condensation reaction of ketone and phenol with the ion exchange resin in aqueous condition for the isomerization of the undesired product and separating the product having higher bisphenol content, wherein said ion exchange resin is aromatic polymer having the sulfonic acid group modified with at least one promoter selected from the compound shown in the structure (I):

##STR00004##

[0026] wherein,

[0027] X represents heteroatoms; and

[0028] n is an integer from 1 to 4.

[0029] Preferably, at least one promoter is the compound shown in the structure (II) or (III):

##STR00005##

[0030] More preferably, the promoter is the compound shown in the structure (II):

##STR00006##

[0031] In one aspect, said promoter further comprises the aminoalkyl mercaptan which may be selected from cysteamine, 2-amino-1-propanethiol, and 3-mercaptopropylamine. Preferably, the aminoalkyl mercaptan is cysteamine.

[0032] Most preferably, the promoter is the mixture of the compound according to the structure (II) and cysteamine.

[0033] In one aspect of the invention, the promoter comprises the aminoalkyl mercaptan in the amount of 10 to 90% by mole of total promoter, preferably 30 to 70% by mole of total promoter.

[0034] In one aspect of the invention, the sulfonic acid group modified with promoter is 10 to 20% of total sulfonic acid group.

[0035] In one aspect, the sulfonic acid group is modified with promoter via ionic bond which may be formed via the nitrogen atom of said promoter and the sulfonic acid group of aromatic polymer.

[0036] Generally, said modification may be performed by mixing between the aromatic polymer having sulfonic acid group and the promoter, wherein water or aromatic hydroxy compound is used as the solvent.

[0037] In one aspect of the invention, the aromatic polymer having sulfonic acid group may be selected from polystyrene having sulfonic acid group or styrene-divinylbenzene copolymer having sulfonic acid group, preferably styrene-divinylbenzene copolymer having sulfonic acid group.

[0038] In one aspect, said styrene-divinylbenzene copolymer having sulfonic acid group may have divinylbenzene in the amount of about 1 to 15%, preferably in the amount of about 10 to 15%.

[0039] In one aspect, said aromatic polymer having sulfonic acid group has particle size in the range of about 500 to 1500 micron, preferably in the range of about 600 to 850 micron.

[0040] In one aspect of the invention, the weight ratio of ion exchange resin to product obtained from the bisphenol preparation is in the range of 1:1 to 1:5, preferably in the range of 1:1 to 1:3.

[0041] In one aspect of the invention, said isomerization reaction is performed at the temperature in the range of 40 to 120° C. and at atmospheric pressure, preferably at the temperature in the range of 60 to 80° C. and at atmospheric pressure.

[0042] In one aspect of the invention, said isomerization reaction is performed in aqueous condition having water content in the range of 0.01 to 3.5% by weight, preferably in the range of 0.05 to 0.5% by weight.

[0043] In one aspect, the product obtained from the bisphenol preparation before occurring isomerization reaction comprises the undesired products which are 4,4′-isopropylidenediphenol and 2,4′-isopropylidenediphenol.

[0044] In one aspect of the invention, the bisphenol preparation from a condensation reaction of ketone and phenol, wherein ketone may be selected from, but not limited to acetone, diethyl ketone, methyl ethyl ketone, ethylmethyl ketone, isobutylmethyl ketone, cyclohexanone, acetophenone, and 1,3-dichloroacetone; and phenol may be selected from, but no limited to unsubstituted phenol, alkylphenol, alkoxyphenol, naphthol, alkylnaphthol, and alkoxynaphthol.

[0045] In one aspect, the ion exchange resin used in isomerization reaction according to the invention may be used in the form of slurry for reaction in batch system or may be used in the form of fixed bed solid for reaction in continuous system.

[0046] In one aspect, the reaction time may be in the range of about 1 to 24 hours for reaction in batch system and reaction in continuous system. The liquid hourly space velocity (LHSV) may be in the range of about 0.015 to 10 hour.sup.−1.

[0047] In one aspect of the invention, the separation of product having higher bisphenol content is the crystallization of the 4,4′-isopropylidenediphenol product in order to separate 4,4′-isopropylidenediphenol having high purity.

[0048] The following examples are for demonstrating the aspects of the invention only and not intended to be limitation of the scope of this invention in any way.

[0049] Preparation of the Promoter for Preparing Ion Exchange Resin According to the Invention

[0050] Compound as Shown in the Structure (II)

[0051] About 5 g of 2-pyridene carboxylic acid and about 6 g of cysteamine hydrochloride were dissolved in about 50 mL of dichloromethane solvent under an argon atmosphere. Then, the mixture solution of about 17 g of dicyclohexyl carbodiimide and about 1 g of 4-dimethylaminopyridene was added into about 20 mL of dichloromethane solvent. The said mixture was stirred at room temperature under an argon atmosphere for about 24 hours. The solid was filtered from the obtained mixture. Then, the filtrated liquid was evaporated under vacuum. After that, the filtrated liquid was crystallized in organic solvent or subjected to the purification using silica column. The obtained solid was separated and dried.

[0052] Preparation of the Ion Exchange Resin According to the Invention

[0053] The styrene-divinylbenzene copolymer type aromatic polymer having sulfonic acid group Amberlyst36 (Am36) with particle size in the range of about 600 to 850 micron was used in the preparation of the ion exchange resin according to the invention.

[0054] The promoter was dissolved in about 20 mL of deionized water and then added into about 20 g of styrene-divinylbenzene copolymer suspended in the deionized water. Then, said mixture was stirred at room temperature for about 1 hour. After stirring, the obtained mixture was packed in the glass column and washed with deionized water. The obtained solid was analyzed for the residual sulfonic acid group by titration method with sodium hydroxide solution in order to determine the sulfonic acid group (SO.sub.3H) content before and after aromatic polymer modification. The percentage of sulfonic acid group modified with promoter could be calculated from the following equation.

[00001]$\mathrm{Percentage}\mathrm{of}\mathrm{sulfonic}\mathrm{acid}\mathrm{group}\mathrm{modified}\mathrm{with}\mathrm{promoter}=\frac{\mathrm{mole}\mathrm{of}{\mathrm{SO}}_{3}H\mathrm{before}\mathrm{modification}-\mathrm{mole}\mathrm{of}{\mathrm{SO}}_{3}H\mathrm{after}\mathrm{modification}}{\mathrm{mole}\mathrm{of}{\mathrm{SO}}_{3}H\mathrm{before}\mathrm{modification}}\times 100$

[0055] Testing of the Isomerization Reaction Using Ion Exchange Resin

[0056] The ion exchange resin according to the invention was used as the catalyst for testing the isomerization efficiency of the product obtained from the bisphenol preparation by the following method.

[0057] Prior to use, the ion exchange resin was dehydrated by contacting about 10 g of the ion exchange resin with about 100 g of phenol at the temperature about 60 to 70° C. for about 15 minutes. This step was repeated for 3 times. Then, about 1.5 g of the obtained ion exchange resin was added into the round bottom flask. About 3 g of product obtained from the bisphenol preparation from a condensation reaction of ketone and phenol was contacted with said ion exchange resin in aqueous condition having desirable water content and then heated at desirable temperature. Then, the isomerization reaction of undesired product was operated until the end of desirable time.

[0058] The followings are the examples for testing of product compositions obtained from isomerization reaction using the ion exchange resin according to the invention, wherein methods and equipment used in testing are methods and equipment being used commonly and not intended to limit the scope of the invention.

[0059] The compositions and amounts of the products were analyzed by High Performance Liquid Chromatography (Shimadzu LC-20AD) using Reverse phase Phenomenex Gemini-NX 5μ C18 column and the solvent system between water and acetonitrile as the mobile phase with a flow rate of about 1 mL/min.

[0060] The % conversion of 2,4′-isopropylidenediphenol (2,4′ BPA), % weight gain of 4,4′-isopropylidenediphenol (4,4′ BPA) and % tar reduction were calculated from the following equations.

[00002]$\%\mathrm{conversion}\mathrm{of}2,4^{\prime }-\mathrm{isopropylidenediphenol}=\frac{\mathrm{signal}\mathrm{of}2,4^{\prime }-\mathrm{isopropylidenediphenol}\mathrm{in}\left(\mathrm{feed}-\mathrm{mixture}\mathrm{after}\mathrm{reaction}\right)}{\mathrm{signal}\mathrm{of}2,4^{\prime }-\mathrm{isopropylidenediphenol}\mathrm{in}\mathrm{feed}}\times 100$$\%\mathrm{weight}\mathrm{gain}\mathrm{of}4,4^{\prime }-\mathrm{isopropylidenediphenol}=\frac{\mathrm{signal}\mathrm{of}4,4^{\prime }-\mathrm{isopropylidenediphenol}\mathrm{in}\left(\mathrm{mixture}\mathrm{after}\mathrm{reaction}-\mathrm{feed}\right)}{\mathrm{signal}\mathrm{of}4,4^{\prime }-\mathrm{isopropylidenediphenol}\mathrm{in}\mathrm{feed}}\times 100$$\%\mathrm{tar}\mathrm{reduction}=\frac{\mathrm{tar}\mathrm{content}\mathrm{in}\mathrm{feed}-\mathrm{tar}\mathrm{content}\mathrm{in}\mathrm{mixture}\mathrm{after}\mathrm{reaction}}{\mathrm{tar}\mathrm{content}\mathrm{in}\mathrm{feed}}\times 100$

TABLE-US-00001 TABLE 1 % conversion of 2,4′-isopropylidenediphenol and % weight gain of 4,4′-isopropylidenediphenol after isomerization reaction using different ion exchange resins Water % conversion of % weight gain content 2,4′- of 4,4′- (% by Temperature Time isopropylidene isopropylidene % tar Sample Promoter weight) (° C.) (hr) diphenol diphenol reduction Comparative — 0.39 80 8 85.1 0 33.5 sample 1 Comparative — 0.14 80 19 85.8 1.9 23.8 sample 2 Comparative — 1.04 80 12 58 2.8 6.5 sample 3 Comparative — 0.39 80 24 82.8 4.4 30.4 sample 4 Comparative cysteamine 0.39 80 24 79.1 1.1 9.7 sample 5 Comparative — 0.39 100 24 91.7 0.2 8.4 sample 6 Sample (II) + 0.39 80 12 80.3 14.5 16.8 according to cysteamine the invention 1 Sample (II) 0.39 80 12 67.4 1.7 8.5 according to the invention 2 Sample (II) + 0.39 80 24 84.8 38.5 21 according to cysteamine the invention 3 Sample (II) + 0.39 100 24 93.5 2.2 24.6 according to cysteamine the invention 4

[0061] From table 1, when comparing the comparative sample 1 to 5 to the sample according to the invention 1 to 4 which were subjected to test efficiency by isomerization reaction at temperature about 80° C., it was found that the ion exchange resin according to the invention gave high percent conversion of 2,4′-isopropylidenediphenol and percent weight gain of 4,4′-isopropylidenediphenol. The ion exchange resin according to the invention using the promoter shown in the structure (II) and cysteamine showed highest efficiency.

[0062] Moreover, when comparing the comparative sample 6 to the sample according to the invention 4 which were subjected to test efficiency by isomerization reaction at temperature about 100° C., it was found that the ion exchange resin according to the invention gave higher percent conversion of 2,4′-isopropylidenediphenol, percent weight gain of 4,4′-isopropylidenediphenol, and percent tar reduction.

[0063] From the results above, it can be said that the ion exchange resin according to the invention gives high efficiency for percent conversion of 2,4′-isopropylidenediphenol, percent weight gain of 4,4′-isopropylidenediphenol, and percent tar reduction as being stated in the objective of this invention.

Best Mode or Preferred Embodiment of the Invention

[0064] Best mode or preferred embodiment of the invention is as provided in the description of the invention.