Water-absorbing, cellular, cross-linked polymers with improved distribution effect, method for their production and their use

• US 6,750,262 B1
• Filed: 09/04/2001
• Issued: 06/15/2004
• Est. Priority Date: 03/03/1999
• Status: Expired due to Fees

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Anstock, Thomas, Hähnle, Hans-Joachim, Schornick, Gunnar, Schröder, Ulrich, Heider, Wolfgang
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US09/926,110
• Time in Patent Office: 1,015 Days
• Field of Search: 521/65, 521/64
• US Class Current: 521/64
• CPC Class Codes: A61L 15/24 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 15/425 Porous materials, e.g. foams or sponges
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: C08J 2207/12 Sanitary use, e.g. diapers, napkins or bandages
• CPC Class Codes: C08J 2300/10 Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• CPC Class Codes: C08J 9/122 Hydrogen, oxygen, CO2, nitrogen or noble gases
• CPC Class Codes: C08J 9/30 by mixing gases into liquid compositions or plastisols, e.g. frothing with air
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C09K 17/20 Vinyl polymers
• CPC Class Codes: C09K 2003/1046 Water-absorbing materials
• CPC Class Codes: C09K 2200/0625 Polyacrylic esters or derivatives thereof
• CPC Class Codes: C09K 2200/0657 Polyethers
• CPC Class Codes: C09K 3/10 Materials in mouldable or extrudable form for sealing or packing joints or covers filling pastes C09D5/34

Abstract

Water-absorbing, expanded, crosslinked polymers obtainable by

(I) foaming a polymerizable aqueous mixture which comprises

(a) monoethylenically unsaturated monomers which contain acidic groups and are optionally neutralized,

(b) optionally other monoethylenically unsaturated monomers,

(c) crosslinkers,

(d) initiators,

(e) 0.1-20% by weight of at least one surfactant,

(f) optionally at least one solubilizer and

(g) optionally thickeners, foam stabilizers, polymerization regulators, fillers and/or cell nucleating agents,

where the foaming takes place by dissolving a gas which is inert to free radicals under a pressure of 2-400 bar in the polymerizable aqueous mixture, and then decompressing the latter to atmospheric pressure, and

(II) polymerizing the foamed mixture to form an expanded hydrogel and, where appropriate, adjusting the water content of the expanded polymer to 1-60% by weight, process for preparing the water-absorbing, expanded, crosslinked polymers and use of these polymers in sanitary articles employed for absorbing body fluids, in dressing material for covering wounds, as sealing material, as soil improver, as soil substitute and as packaging material.

Claims

1. An expanded, crosslinked polymer which has a free absorption speed (FAS) for a 0.9% aqueous sodium chloride solution of from 4.0 to 100 g/g sec, obtained by

(I) foaming a polymerizable aqueous mixture which comprises

(a) one or more monoethylenically unsaturated monomers which contain acidic groups or monoethylenically unsaturated monomers which contain acidic groups neutralized with alkali metal bases, ammonia or amines,

(c) one or more crosslinkers,

(d) one or more initiators and

(e) 0.1-20% by weight of at least one surfactant,

where the foaming takes place by dissolving a gas which is inert to free radicals under a pressure of 2-400 bar in the polymerizable aqueous mixture, and then decompressing the aqueous mixture to atmospheric pressure, and

(II) polymerizing the foamed mixture to form an expanded hydrogel.

2. The polymer as claimed in claim 1, obtained by

(I) foaming a polymerizable aqueous mixture which comprises

(a) one or more monoethylenically unsaturated monomers which contain acidic groups from 15 to 90 mol % neutralized with alkali metal bases, ammonia or amines,

(b) one or more other monoethylenically unsaturated monomers,

(c) one or more crosslinkers,

(d) one or more initiators,

(e) 0.1-20% by weight of at least one surfactant,

(f) at least one solubilizer and

(g) one or more thickeners, foam stabilizers, polymerization regulators, fillers and/or cell nucleating agents,

where the foaming takes place by dissolving a gas which is inert to free radicals under a pressure of 2-400 bar in the polymerizable aqueous mixture, and then decompressing the aqueous mixture to atmospheric pressure, and

(II) polymerizing the foamed mixture to form an expanded hydrogel and adjusting the water content of the expanded polymer to 1-60% by weight.

3. The polymer as claimed in claim 1, which is obtained by neutralizing the monomers (a) which contain acidic groups with tertiary alkanolamines and/or by neutralizing the free acidic groups of the expanded hydrogel after the polymerization with at least one alkanolamine, wherein the degree of neutralization is at least 20 mol % in each case.

4. The polymer as claimed in claim 1, wherein the degree of neutralization is at least 40 mol %.

5. The polymer as claimed in claim 1, which has a vertical wicking time (VWT=time for a 0.9% by weight aqueous sodium chloride solution to spread vertically in a foam) of 0.2-120 seconds for a height of 4 cm.

11. A method comprising

absorbing body fluids with one or more of a dressing material for covering wounds, a sealing material, a soil improver, a soil substitute or a packaging material comprising the polymer as claimed in claim 1.

12. A hygiene article employed to absorb body fluids, in dressing material for covering wounds, as sealing material, as soil improver, as soil substitute and as packaging material comprising the water-absorbing, expanded, crosslinked polymers as claimed in claim 1.

13. The polymer as claimed in claim 1, wherein at least 1.0 g of the inert gas is dissolved per kilogram of the polymerizable mixture.

15. The polymer as claimed in claim 1, wherein the inert gas is selected from the group consisting of carbon dioxide, nitrogen, dinitrogen monoxide and mixtures thereof.

17. The polymer as claimed in claim 1, wherein the decompressing is carried out in one or more pressure drops.

6. A process for producing expanded, crosslinked polymers, comprising

foaming a polymerizable mixture of

(a) one or more monoethylenically unsaturated monomers which contain acidic groups or monoethylenically unsaturated monomers which contain acidic groups neutralized with alkali metal bases, ammonia or amines,

(c) one or more crosslinkers,

(d) one or more initiators and

(e) 0.1-20% by weight of at least one surfactant,

to form a foam in a first stage with a gas which is inert to free radicals, and in a second stage polymerizing the foam to form an expanded hydrogel, where in the first stage a gas which is inert to free radicals is dissolved under a pressure of 2-400 bar in the polymerizable aqueous mixture, and the aqueous mixture is then decompressed to atmospheric pressure to form a foam.

7. The process as claimed in claim 6, wherein the polymerizable aqueous mixture is saturated with carbon dioxide or nitrogen under a pressure of 5-40 bar.

8. The process as claimed in claim 6, wherein at least 20 mol % of the monomers (a) which contain acidic groups are neutralized with tertiary alkanolamines and/or the free acidic groups of the expanded hydrogel are at least 20 mol % neutralized with at least one alkanolamine after the polymerization.

9. The process as claimed in claim 6, wherein at least 40 mol % of the monomers (a) which contain acidic groups are neutralized with tertiary alkanolamines and/or the free acidic groups of the expanded hydrogel are at least 40 mold neutralized with at least one alkanolamine after the polymerization.

10. The process as claimed in claim 6, wherein triethanolamine, ethanolamine and/or N,N,N′

,N′

-tetra(hydroxyethyl)ethylenediamine are employed as alkanolamines.

14. The process as claimed in claim 6, wherein at least 1.0 g of the inert gas is dissolved per kilogram of the polymerizable mixture.

16. The process as claimed in claim 6, wherein the inert gas is selected from the group consisting of carbon dioxide, nitrogen, dinitrogen monoxide and mixtures thereof.

18. The process as claimed in claim 6, wherein the decompressing is carried out in one or more pressure drops.