Hydrophilic, highly swellable hydrogels

• US 5,331,059 A
• Filed: 11/12/1992
• Issued: 07/19/1994
• Est. Priority Date: 11/22/1991
• Status: Expired due to Fees

• Current Assignee: Cassella Aktiengesellschaft (Sanofi )
• Original Assignee: Cassella Aktiengesellschaft (Sanofi )
• Inventors: Funk, Rudiger, Ebert, Gerlinde, Riegel, Ulrich, Engelhardt, Friedrich, Kleiner, Hanss-Jerg
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): MERRIAM, ANDREW EDWIN
• Application Number:
  US07/974,621
• Time in Patent Office: 614 Days
• Field of Search: 526/278, 525/340, 525/330.4, 525/329.8, 525/287, 525/193, 524/530, 524/916
• US Class Current: 525/340
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: C08F 8/40 Introducing phosphorus atoms or phosphorus-containing groups
• CPC Class Codes: C08G 59/304 containing phosphorus
• CPC Class Codes: C08K 5/5373 containing heterocyclic rings not representing cyclic esters of phosphonic acids
• CPC Class Codes: Y10S 524/916 Hydrogel compositions

Abstract

The present invention relates to a hydrophilic, highly swellable hydrogel based on (co)polymerized hydrophilic monomers or based on graft (co)polymers, characterized in that it has been surface-modified by means of a mixture of

A) one or more diglycidyl phosphonates and

B) one or more other reactive compounds which are capable of reacting with the functional groups in the polymer, to a process for the preparation thereof, to the use thereof, and to diglycidyl phosphonate-containing crosslinking agent mixtures.

Claims

1. Hydrophilic, highly swellable hydrogel derived from hydrophilic monomers in (co)polymerized form or derived from graft (co)polymers, in which the hydrogel is further surface modified by means of a mixture of

A) one or more diglycidyl phosphonates of general formula I ##STR9## in which R is alkyl, alkenyl or aryl, each of which is optionally substituted, and

B) one or more other reactive compounds which are capable of reacting with the functional groups in the polymer.

2. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R is (C₁ -C₁₈)-alkyl;

(C₃ -C₈)-cycloalkyl;

a group of the general formula II ##STR10## in which R¹ and R², independently of one another, are hydrogen or (C₁ -C₄)-alkyl;

or a group of the general formula III ##STR11## in which R³ is hydrogen, halogen or (C₁ -C₄)-alkyl, and component B) is one or more (poly)glycidyl ethers and/or one or more alkoxysilyl compounds and/or one or more polyaziridines and/or one or more polyamines and/or one or more polyamidoamines.

3. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, decyl, stearyl and cyclohexyl.

4. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R₁ or R₂ is methyl.

5. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R₃ is in the 2-, 3- or 4-position with respect to the carbon-phosphorus bond.

6. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R₃ is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, iodine and hydrogen.

7. Hydrophilic, highly swellable hydrogel according to claim 1, wherein R₃ is selected from the group consisting of methyl, chlorine, and hydrogen.

8. Hydrophilic, highly swellable hydrogel according to claim 1, wherein the compounds of general formula I are selected from the group consisting of diglycidyl methylphosphonate, diglycidyl n-propylphosphonate, diglycidyl stearylphosphonate and diglycidyl decanephosphonate.

9. Hydrophilic, highly swellable hydrogel according to claim 2, wherein the (poly)glycidyl ethers are monoethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether.

10. Hydrophilic, highly swellable hydrogel according to claim 2, wherein the (poly)glycidyl ethers are nonethylene glycol diglycidyl ether, monopropylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether.

11. Hydrophilic, highly swellable hydrogel according to claim 2, wherein the alkoxysilyl compounds are aminoalkylalkoxysilanes.

12. Hydrophilic, highly swellable hydrogel according to claim 11, wherein the aminoalkylalkoxysilanes are selected from the group consisting of 3-aminopropyltriethoxysilane, trimethoxysilyl -propyldiethylenetriamine,N-aminoethylaminopropyltrimethoxysilane, aminoethylaminomethylphenethyltrtmethoxysilane and glycidylalkoxysilanes.

13. Hydrophilic, highly swellable hydrogel according to claim 1, wherein the proportion of B) in the mixture of compound(s) of the general formula I and compound(s) as in B) Is from 0.5 to 90% by weight.

14. Hydrophilic, highly swellable hydrogel according to claim 1, wherein the proportion of B) in the mixture of compound(s) of the general formula I and compound(s) as in B) Is from 1 to 60% by weight.

15. Hydrophilic, highly swellable hydrogel according to claim 1, wherein the proportion of the mixture of compound(s) of the general formula I and compound(s) as in B) is from 0.01 to 10% by weight.

16. Hydrophilic, highly swellable hydrogel according to claim 1, wherein the proportion of the mixture of compound(s) of the general formula I and compound(s) as In B) is from 0.05 to 3% by weight.

17. An adsorbent for water and aqueous solutions comprising the hydrophilic, highly swellable hydrogel as claimed in claim 1.

18. Process for the preparation of a hydrophilic, highly swellable hydrogel according to claim 1, wherein the polymers made from (co)polymerized hydrophilic monomers or graft (co)polymers in solid form, having a particle size distribution of between about 20 and about 1,000 μ

m, are treated in a mixer with a mixture of one or more compounds of the general formula I and one or more compounds as in B).

19. Process for the preparation of a hydrophilic, highly swellable hydrogel according to claim 18, wherein the particle size distribution is between about 100 and about 850 μ

m.

22. A method for the production of hygiene articles comprising incorporating the hydrophilic, highly swellable hydrogel as claimed in claim 1 into said hygiene articles.

20. Crosslinking agent mixture comprising

A) one or more diglycidyl phosphonates of the general formula I ##STR12## in which R is alkyl, alkenyl or aryl, each of which is optionally substituted, and

B) one or more other reactive compounds which are capable of reacting with the functional groups of the polymer to be crosslinked.

21. Crosslinking agent mixture according to claim 20, comprising

A) one or more diglycidyl phosphonates of the general formula I ##STR13## in which R is (C₁ -C₁₈)-alkyl;

(C₃ -C₈)-cycloalkyl;

a group of the general formula II ##STR14## in which R¹ and R² independently of one another, are hydrogen or (C₁ -C₄)-alkyl;

or a group of the general formula III ##STR15## in which R³ is hydrogen, halogen or (C₁ -C₄)-alkyl, and B) one or more (poly)glycidyl ethers and/or one or more alkoxysilyl compounds and/or one or more polyaziridines and/or one or more polyamines and/or one or more polyamidoamines.

23. The surface modification of hydrophilic monomers in (co)polymerized for or of graft (co)polymers comprising reacting said polymers with the crosslinking agent mixture as claimed in claim 20.