SUPERABSORBENT POLYMERS AND METHODS OF MAKING THE SAME

• US 20130253149A1
• Filed: 05/17/2013
• Published: 09/26/2013
• Est. Priority Date: 08/22/2006
• Status: Active Grant

• Current Assignee: Andreas Sabbagh, Axel Hengstermann, Franz-Felix Kuppinger, Guido Stochniol, Gunther Bub, Jurgen Mosler
• Original Assignee: Andreas Sabbagh, Axel Hengstermann, Franz-Felix Kuppinger, Guido Stochniol, Gunther Bub, Jurgen Mosler
• Inventors: Kuppinger, Franz-Felix, Hengstermann, Axel, Stochniol, Guido, Bub, Gunther, Mosler, Jurgen, Sabbagh, Andreas
• Granted Patent: US 8,895,683 B2
• Time in Patent Office: Days
• US Class Current: 526/75
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 51/43 by change of the physical state, e.g. crystallisation
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C08F 120/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

In one aspect, a process for the preparation of a superabsorbent polymer is described herein. In some embodiments, the process comprises (I) preparing acrylic acid, wherein the process comprises (a1) provision of a fluid F1 having a composition comprising from about 5 to about 20 wt. % of hydroxypropionic acid, salts thereof, or mixtures thereof; from about 0.1 to about 5 wt. % of inorganic salts; from about 0.1 to about 30 wt. % of organic compounds which differ from hydroxypropionic acid; from 0 to about 50 wt. % of solids; and from about 20 to about 90 wt. % of water; (a2) dehydration of said hydroxypropionic acid to give a fluid F2 containing acrylic acid; and (a3) purification of said fluid F2 to give a purified acrylic acid phase comprising acrylic acid having a purity of at least 70 wt. %; and (II) polymerizing the acrylic acid of (I) to form a superabsorbent polymer.

Claims

1-14. -14. (canceled)

15. A superabsorbent polymer made by the process comprising the steps of:

I) preparing acrylic acid wherein the acrylic acid is made from a fluid F1 containing 2-hydroxypropionic acid wherein said fluid F1 is obtained by a process comprising the process steps of i) preparation of 2-hydroxypropionic acid from carbohydrates to give an aqueous phase containing 2-hydroxypropionic acid and solids including microorganisms, and ii) separating off of the solids from said aqueous phase, wherein the process of preparing acrylic acid comprises the process steps;

(a1) provision of said fluid F1 containing a 2-hydroxypropionic acid;

wherein said fluid F1 is aqueous, and has a composition comprising

(C1-1) from about 5 to about 20 wt. % of 2-hydroxypropionic acid, salts thereof, or mixtures thereof,

(C1-2) from about 0.1 to about 5 wt. % of inorganic salts,

(C1-3) from about 0.1 to about 30 wt. % of organic compounds which differ from 2-hydroxypropionic acid,

(C1-4) from 0 to about 50 wt. % of solids, and

(C1-5) from about 20 to about 90 wt. % of water,

wherein the sum of components (C1-1) to (C1-5) is 100 wt. %;

(a2) dehydration of said 2-hydroxypropionic acid to give a fluid F2 containing acrylic acid wherein the dehydration comprises a reactive distillation and the dehydration is carried out in a CO₂ atmosphere, or an inorganic acid, or both; and

(a3) purification of said fluid F2 containing acrylic acid by crystallization to give a purified acrylic acid phase wherein said purified acrylic acid phase comprises acrylic acid having a purity of at least 70 wt. %; and

II) polymerizing the acrylic acid of I) in the presence of a crosslinker and a neutralization agent to form a superabsorbent polymer.

16. The superabsorbent polymer of claim 15 wherein said dehydration is carried out in at least two reactors, comprising the following process steps:

i) heating of said fluid F1 in at least one first reactor in the presence of a homogeneous or heterogeneous catalyst to give a first aqueous fluid containing acrylic acid under a pressure π

1;

ii) introduction of said first aqueous fluid into a further reactor; and

iii) heating of said first aqueous fluid introduced into said further reactor in the presence of a catalyst under a pressure π

2 to give said fluid F2;

wherein said pressure π

2 and said pressure π

1 are not equal.

17. The superabsorbent polymer of claim 16, wherein said pressure π

2 is lower than said pressure π

1.

18. The superabsorbent polymer of claim 15, wherein said crystallization is selected from the group consisting of a suspension crystallization or a layer crystallization.

19. The superabsorbent polymer of claim 15 further comprising cooling said fluid F1 to a maximum to the temperature of the triple eutectic point of a composition of acrylic acid, water and 2-hydroxypropionic acid.

20. The superabsorbent polymer of claim 15 wherein process step (a3) comprises obtaining a first crystal phase;

wherein said first crystal phase comprises;

i) at least about 5 wt. % of acrylic acid,

ii) at least about 40 wt. % of water, and

iii) at most about 10 wt. % of 2-hydroxypropionic acid.

21. The superabsorbent polymer of claim 15 wherein the purification is carried out by an at least two-stage crystallization.

22. The superabsorbent polymer of claim 15 wherein process step (a3) comprises the following process steps:

(a3-1) crystallization of said fluid F2 in a first crystallization stage to give a crystal phase K1 and a mother liquor M1, wherein said crystal phase K1 comprises;

i) from about 5 to about 60 wt. % of acrylic acid,

ii) from 39.9 to about 95 wt. % of water, and

iii) from about 0.1 to about 10 wt. % of by-products which differ from water and acrylic acid,

and wherein the sum of the amounts by weight of acrylic acid, water and by-products is 100 wt. %,

(a3-2) separating off of said crystal phase K1 from said mother liquor M1,

(a3-3) melting of said crystal phase K1 from said first crystallization stage,

(a3-4) renewed crystallization of said melted crystal phase K1 in a second crystallization stage to give a crystal phase K2 and a mother liquor M2, wherein said crystal phase K2 comprises;

i) from about 8 to about 35 wt. % of acrylic acid,

ii) from about 60 to about 90 wt. % of water, and

iii) from about 2 to about 5 wt. % of by-products which differ from water and acrylic acid,

wherein the sum of the amounts by weight of acrylic acid, water and by-products is 100 wt. %,

(a3-5) separating off of said crystal phase K2 from said mother liquor M2,

(a3-6) crystallization of said mother liquor M2 in a third crystallization stage to give a crystal phase K3 and a mother liquor M3, wherein said crystal phase K3 comprises;

i) from about 25 to about 55 wt. % of acrylic acid,

ii) from 44.5 to about 70 wt. % of water, and

iii) from about 0.5 to about 5 wt. % of by-products which differ from water and acrylic acid,

wherein the sum of the amounts by weight of acrylic acid, water and by-products is 100 wt. %, and

(a3-7) separating off of said crystal phase K3 from said mother liquor M3, a purified phase containing acrylic acid crystals being obtained.

23. The superabsorbent polymer of claim 22 wherein the mother liquor obtained in process step (a3-2) is fed back into step (a1).

24. The superabsorbent polymer of claim 15 wherein said purified acrylic acid phase has a purity of at least about 40% with respect to the acrylic acid.

25. The superabsorbent polymer of claim 15 wherein said 2-hydroxypropionic acid in said fluid F1 or the acrylic acid in said fluid F2 is converted into its protonated form by the addition of acids before carrying out at least one of process steps (a2) or (a3).