Water-absorbent polymer having improved properties

• US 5,447,727 A
• Filed: 10/14/1992
• Issued: 09/05/1995
• Est. Priority Date: 10/14/1992
• Status: Expired due to Fees

• Current Assignee: Stockhausen GmbH
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Graham, Andrew T.
• Primary Examiner(s): Kulkosky, Peter F.
• Application Number:
  US07/960,675
• Time in Patent Office: 1,056 Days
• Field of Search: 526/323, 526/326, 526/323.1, 526/322, 526/318.3, 526/323.2, 526/330, 526/306, 526/307.1, 526/330.3, 526/330.5, 526/384, 526/385, 424/487, 424/443
• US Class Current: 424/487
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: C08F 20/00 Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 22/00 Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C

Abstract

The subject invention provides a surface-crosslinked water-absorbent polymer having improved properties. The subject invention further pertains to a process for preparing such a polymer. Through the use of a preferred primary crosslinking agent coupled with surface crosslinking, desirable absorptive properties are achieved. Suitable primary crosslinking agents include methylenebisacrylamide, bis(acrylamido)acetic acid and its salts, allyl acrylate, allyl methacrylate and esters or amides having both a vinyl and an allyl functionality.

Claims

1. A water-absorbent polymeric material comprising a crosslinked polymer of a partially neutralized α

,β

-ethylenically unsaturated monomer, the crosslinked polymer being crosslinked with a primary crosslinking agent selected from the groups consisting of, bis(acrylamido)acetic acid and its salts, allyl acrylate, allyl methacrylate and esters or amides having both a vinyl and an allyl functionality, the crosslinked polymer being additionally crosslinked with a surface crosslinking agent selected from the group consisting of polyhydroxy compounds, polyglycidyl ether compounds, polyfunctional aziridine compounds, polyfunctional amine compounds, and polyfunctional isocyanate compounds, whereupon the molecular chains existing in the vicinity of the surface of the polymer are crosslinked.

2. The water-absorbent polymeric material of claim 1, wherein the surface crosslinking agent is a polyhydroxy compound.

3. The water-absorbent polymeric material of claim 2, wherein the polyhydroxy compound is selected from the group consisting of diethylene glycol, triethylene glycol, glycerol, propylene glycol, trimethylolpropane, pentaerythritol, sorbitol, and polyethylene glycol.

4. The water-absorbent polymeric material of claim 2, wherein the polyhydroxy compound is glycerol.

5. The water-absorbent polymeric material of claim 1, wherein the primary crosslinking agent is allyl methacrylate.

6. The water-absorbent polymeric material of claim 1, wherein the surface crosslinking agent is provided in an amount from about 0.00025 to about 2 weight percent, based on the weight of the crosslinked polymer.

13. The process of claim 1, wherein the drying of step (b) occurs at a temperature from about 100°

to about 175°

C.

25. A method for using the aqueous fluid absorbent material of claim 1 comprising incorporating the absorbent material into a personal care device.

7. A process for preparing an aqueous fluid absorbent material comprising:

(a) preparing a crosslinked polymer of a partially neutralized α

,β

-ethylenically unsaturated monomer, the crosslinked polymer being crosslinked with a primary crosslinking agent selected from the groups consisting of, bis(acrylamido)acetic acid and its salts, allyl acrylate, allyl methacrylate and esters or amides having both a vinyl and an allyl functionality;

(b) contacting the crosslinked polymer with a surface crosslinking agent selected from the group consisting of polyhydroxy compounds, polyglycidyl ether compounds, polyfunctional aziridine compounds, polyfunctional amine compounds, and polyfunctional isocyanate compounds, under conditions such that the surface crosslinking agent coats the crosslinked polymer without substantial penetration into the interior of the crosslinked polymer to form a coated crosslinked polymer; and

(c) heating the coated crosslinked polymer under conditions such that the surface crosslinking agent reacts with crosslinked polymer so as to crosslink the surface of the coated crosslinked polymer.

8. The process of claim 7, wherein the crosslinked polymer exists as a hydrogel comprising from about 20 to about 95 percent crosslinked polymer and from about 5 to about 80 percent water at the contacting of step (b).

9. The process of claim 7, wherein the crosslinked polymer exists as a powder having a moisture content less than about 5 weight percent at the contacting of step (b).

10. The process of claim 7, wherein the surface crosslinking agent is provided in a composition which comprises the surface crosslinking agent, and which optionally contains one or more constituents selected from the group consisting of water, an organic solvent, and a surfactant.

11. The process of claim 10, wherein the composition comprises from about 50 to about 100 percent polyhydroxy compound and from about 0 to about 50 percent water, the composition being free from organic solvent.

12. The process of claim 8, wherein the process further comprises:

(d) drying the coated crosslinked polymer, such that the water retained within the hydrogel is removed but such that the surface crosslinking agent does not react with the coated crosslinked polymer, the drying occurring after the contacting of step (b) but prior to the heating of step (c).

14. The process of claim 12, wherein the process further comprises:

(e) reducing the particle size of the coated crosslinked polymer by mechanical means after the drying of step (d) but before the heating of step (c).

15. The process of claim 14, wherein the reducing of the particle size results in average particle diameters less than about 0.8 mm.

16. The process of claim 8, wherein the process further comprises:

(d) drying the crosslinked polymer to a moisture content less than about 15 percent prior to the contacting of step (b).

17. The process of claim 16, wherein the drying of step (b) occurs at a temperature from about 100°

to about 175°

C.

18. The process of claim 16, wherein the process further comprises:

(e) reducing the particle size of the coated crosslinked polymer by mechanical means after the contacting of step (b) but before the heating of step (c).

19. The process of claim 18, wherein the reducing of the particle size results in average particle diameters less than about 0.8 mm.

20. The process of claim 7, wherein the heating occurs at a temperature from about 175°

to about 210°

C. for from about 5 to about 75 minutes.

21. The process of claim 7, wherein the surface crosslinking agent is provided at a level of at least about 200 ppm based on the weight of the water-absorbent resin.

22. The process of claim 7, wherein the surface crosslinking agent is provided at a level of at least about 500 ppm based on the weight of the water-absorbent resin.

23. The process of claim 7, wherein the surface crosslinking agent is provided at a level of at least about 1000 ppm based on the weight of the water-absorbent resin.

24. An aqueous fluid absorbent material produced in accordance with the process of claim 7.