Ion exchange resin for producing bisphenol, and a method for producing bisphenol using said ion exchange resin

Patent metadata

Field	Value
Publication number	US-10851230-B2
Application number	US-201616060162-A
Country	US
Kind code	B2
Filing date	Oct 31, 2016
Priority date	Dec 9, 2015
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

Abstract

This invention relates to an ion exchange resin for producing bisphenol with high percent conversion and high percent selectivity to bisphenol, especially 4,4′ isopropyhdenediphenol, wherein said ion exchange resin comprising aromatic polymer having sulfonic acid group modified with at least one promoter selected from compounds shown in the structure (I), (II), (III), (IV) or its amine salt: wherein R represents hydrocarbon unit with 1 to 6 carbon atoms selected from alkyl group, alkenyl group, alkynyl group, phenyl group, or optionally hydrocarbon containing carbonyl group having 1 to 6 carbon atoms; X represents heteroatom; n is an integer number from 1 to 4.

First claim

The invention claimed is:

1. An ion exchange resin for producing bisphenol comprising aromatic polymer having a sulfonic acid group modified with at least one promoter selected from the group consisting of compounds shown in the structure (I), (IV) and amine salt thereof:

wherein
R represents hydrocarbon unit having 1 to 6 carbon atoms selected from the group consisting of alkyl group, alkenyl group, alkynyl group, phenyl group, and a hydrocarbon containing carbonyl group having 1 to 6 carbon atoms;
x represents heteroatom;
n is an integer number from 1 to 4.

2. The ion exchange resin according to claim 1 , wherein at least one promoter is selected from the group consisting of compounds shown in the structure (V), (VI), (X), and amine salt thereof:

3. The ion exchange resin according to claim 1 , wherein the promoter is a compound as shown in the structure (V) or amine salt thereof

4. The ion exchange resin according to claim 1 , wherein the promoter further comprises aminoalkyl mercaptan or amine salt thereof.

5. The ion exchange resin according to claim 4 , wherein aminoalkyl mercaptan is cysteamine.

6. The ion exchange resin according to claim 4 , wherein aminoalkyl mercaptan or its amine salt is used in the amount of 10 to 90% by mole of total promoter.

7. The ion exchange resin according to claim 6 , wherein aminoalkyl mercaptan or its amine salt is used in the amount of 30 to 70% by mole of total promoter.

8. The ion exchange resin according to claim 1 , wherein the sulfonic acid group modified with promoter is 5 to 30% of total sulfonic acid group.

9. The ion exchange resin according to claim 8 , wherein the sulfonic acid group modified with promoter is 10 to 20% of total sulfonic acid group.

10. The ion exchange resin according to claim 1 , wherein the sulfonic acid group is modified with promoter through ionic bond.

11. The ion exchange resin according to claim 1 , wherein the aromatic polymer containing sulfonic acid group is selected from the group consisting of polystyrene having sulfonic acid group and styrene-divinylbenzene copolymer having sulfonic acid group.

12. The ion exchange resin according to claim 11 , wherein the aromatic polymer containing sulfonic acid group is styrene-divinylbenzene copolymer having sulfonic acid group.

13. The ion exchange resin according to claim 12 , wherein the styrene- divinylbenzene copolymer having sulfonic acid group has divinylbenzene in the amount of 1 to 10%.

14. The ion exchange resin according to claim 13 , wherein the styrene- divinylbenzene copolymer having sulfonic acid group has divinylbenzene in the amount of 1 to 4%.

15. The ion exchange resin according to claim 1 , wherein the aromatic polymer containing sulfonic acid group has particle size from 500 to 1500 micron.

16. The ion exchange resin according to claim 15 , wherein the aromatic polymer having sulfonic acid group has particle size from 850 to 1400 micron.

17. The ion exchange resin according to claim 1 , wherein the compound according to structure (I) or amine salt of said compound is prepared by the following step:
(a) mixing monocarboxylic acid and mercapto compound in a mole ratio of monocarboxylic acid to mercapto compound from 1:1 to 1:2; and
(b) adding carbodiimide and basic solution into the mixture obtained from step (a).

18. The ion exchange resin according to claim 17 , wherein the mercapto compound in step (a) is mercaptoamine or mercaptoalcohol.

19. The ion exchange resin according to claim 18 , wherein the mercaptoamine is selected from the group consisting of cysteamine hydrochloride, 2-amino-1-propanethiol, 2-amino-1-propanethiol hydrochloride, 3-mercaptopropylamine hydrochloride, 3-amino-2-methyl-1-propanethiol, 3-amino-1-butanethiol, 3-amino-2-butanethiol, 4-amino-2-butanethiol hydrochloride, 3-amino-1-butanethiol hydrochloride, 3-amino-2,2-dimethyl-1-propanethiol, 3-amino-1-pentanethiol, 3-amino-1-pentanethiol hydrochloride, 3-amino-3-methyl-1-butanethiol, and 3-amino-3-methyl -1-1-butanethiol hydrochloride.

20. The ion exchange resin according to claim 19 , wherein the mercaptoamine is cysteamine hydrochloride.

21. The ion exchange resin according to claim 18 , wherein the mercaptoalcohol is selected from the group consisting of mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 2,3-mercaptopropanol, 2-mercaptobutanol, 3-mercaptobutanol, and 3-mercapto-2-butanol.

22. The ion exchange resin according to claim 21 , wherein the mercaptoalcohol is mercaptoethanol.

23. The ion exchange resin according to claim 17 , wherein the carbodiimide in step (b) is selected from the group consisting of N,N′- dicyclohexylcarbodiimide, N,N′-diisopropylcarbodiimide, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride, N-Methyl-N′-tert-butyl carbodiimide, N-ethyl-N′-tert- butylcarbodiimide, N-cyclohexyl-N′-tert-butylcarbodiimide, and 1,3-bis(2,2-dimethyl-1,3- dioxolan-4-ylmethyl)carbodiimide.

24. The ion exchange resin according to claim 23 , wherein the carbodiimide is N,N′-dicyclohexylcarbodiimide.

25. The ion exchange resin according to claim 17 , wherein the basic solution in step (b) is selected from the group consisting of pyridine, 4- dimethylaminopyridine, 2,4,6-trimethylpyridine, diisopropyl ethylamine, N- methylmorpholine, trimethylamine, and N,N-dimethylaniline.

26. The ion exchange resin according to claim 25 , wherein the basic solution in step (b) is 4-dimethylaminopyridine.

27. A method for producing bisphenol from phenol and ketone using the ion exchange resin, wherein the ion exchange resin comprising aromatic polymer having a sulfonic acid group modified with at least one promoter selected from the group consisting of compounds shown in the structure (I), (III), (IV) and amine salt thereof:

wherein R represents hydrocarbon unit having 1 to 6 carbon atoms selected from the group consisting of alkyl group, alkenyl group, alkynyl group, phenyl group, and a hydrocarbon containing carbonyl group having 1 to 6 carbon atoms;
x represents heteroatom;
n is an integer number from 1 to 4.

28. The method according to claim 27 , wherein the phenol is unsubstituted phenol, the ketone is acetone, and the bisphenol is bisphenol A.

Assignees

• Ptt Global Chemical Public Co Ltd

Inventors

• Pengpanich Sitthiphong
• Pornsuriyasak Papapida
• Tang-Amornsuksan Suchada

Classifications

• C08L25/08 Primary

  Copolymers of styrene (C08L29/08, C08L35/06, C08L55/02 take precedence) · CPC title

• B01J31/08 Primary

  Ion-exchange resins · CPC title

• C08K5/3432

  Six-membered rings · CPC title

• C07C39/16

  Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes · CPC title

• C07C37/20

  using aldehydes or ketones · CPC title