Method for producing compositions containing interparticle crosslinked aggregates

• US 5,492,962 A
• Filed: 04/18/1994
• Issued: 02/20/1996
• Est. Priority Date: 04/02/1990
• Status: Expired due to Term

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Berg, Charles J., Lahrman, Frank H., Roe, Donald C.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Cheng, Wu C.
• Application Number:
  US08/228,947
• Time in Patent Office: 673 Days
• Field of Search: 524/557, 524/556, 524/555, 524/563, 524/565, 525/54.26
• US Class Current: 524/556
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents

Abstract

Methods of producing particulate, absorbent, polymeric compositions comprising interparticle crosslinked aggregates. In the methods of the present invention, an interparticle crosslinking agent is applied onto precursor particles; the precursor particles are physically associated to form a multiplicity of aggregates; and the interparticle crosslinking agent is reacted with the polymer material of the precursor particles of the aggregates, while maintaining the physical association of the precursor particles, to form crosslink bonds between the precursor particles to form interparticle crosslinked aggregates. The interparticle crosslinked aggregates are formed to such an extent that the mass average particle size of the polymeric composition is at least about 25% greater than the mass average particle size of the precursor particles.

Claims

1. A method for producing a particulate, absorbent, polymeric composition comprising interparticle covalently crosslinked aggregates, said method comprising the steps of:

(a) providing substantially dry precursor particles of substantially water-insoluble, absorbent, hydrogel-forming, polymer material;

said polymer material of said precursor particles being a slightly network crosslinked product of a polymer selected from the group consisting of hydrolyzed starch/acrylonitrile graft copolymer, partially neutralized starch/acrylonitrile acid graft copolymer, starch-acrylic acid graft copolymer, partially neutralized starch-acrylic acid graft copolymer, saponified vinyl acetate-acrylic ester copolymers, hydrolyzed acrylonitrile or acrylamide copolymers, and partially neutralized polyacrylic acid;

(b) applying (i) an interparticle crosslinking agent and (ii) 0.01 to about 60 parts by weight per 100 parts by weight of said precursor particles of water, a hydrophilic organic solvent, or a mixture thereof onto said precursor particles;

provided that when water is applied to said precursor particles it is used in a proportion of from about 0.1 parts to about 10 parts by weight per 100 parts by weight of the precursor particles;

said interparticle crosslinking agent being capable of reacting with said polymer material of said precursor particles;

said interparticle crosslinking agent being selected from the group consisting of polyhydric alcohol compounds, polyglycidyl ether compounds, polyfunctional aziridine compounds, polyfunctional amine compounds, or polyfunctional isocyanate compounds;

(c) forming a multiplicity of aggregates of said precursor particles; and

(d) reacting said interparticle crosslinking agent with said polymer material of said precursor particles of said aggregates, while insuring minimal dissociation forces or stresses are introduced during the reaction step, to form covalent crosslink bonds between said precursor particles to form interparticle crosslinked aggregates, said interparticle crosslinked aggregates being present in the polymeric composition in an amount such that the polymeric composition has a mass average particle size at least about 25% greater than the mass average particle size of said precursor particles.

2. The method of claim 1 comprising the steps of:

(b) applying an interparticle crosslinking agent onto said precursor particles;

(c) subsequently physically associating said precursor particles to form a multiplicity of aggregates; and

(d) subsequently reacting said interparticle crosslinking agent with said aggregates, while maintaining the physical association of said precursor particles, to form crosslink bonds between said precursor particles.

3. The method of claim 1 comprising the steps of:

(c) physically associating said precursor particles to form a multiplicity of aggregates;

(b) subsequently applying an interparticle crosslinking agent onto said aggregates; and

(d) subsequently reacting said interparticle crosslinking agent with said aggregates, while maintaining the physical association of said precursor particles, to form crosslink bonds between said precursor particles.

4. The method of claim 1 comprising the steps of:

(b) applying an interparticle crosslinking agent onto said precursor particles;

(c) simultaneously physically associating said precursor particles to form a multiplicity of aggregates; and

(d) subsequently reacting said interparticle crosslinking agent with said aggregates, while maintaining the physical association of said precursor particles, which are sufficient to form crosslink bonds between said precursor particles.

5. The method of claim 1 comprising the steps of:

(b) applying an interparticle crosslinking agent onto said precursor particles.

(c) simultaneously physically associating said precursor particles to form a multiplicity of aggregates; and

(d) simultaneously reacting said interparticle crosslinking agent with said aggregates, while maintaining the physical association of said precursor particles, which are sufficient to form crosslink bonds between said precursor particles.

6. The method of claim 1 wherein said interparticle crosslinking agent is mixed with water, a hydrophilic organic solvent, or mixtures thereof.

7. The method of claim 6 wherein step (c) comprises the steps of:

(i) applying an associating agent onto said precursor particles, and

(ii) physically contacting said precursor particles to form a multiplicity of aggregates.

8. The method of claim 7 wherein said associating agent is selected from the group consisting of water, a hydrophilic organic solvent, an interparticle crosslinking agent, or mixtures thereof.

9. The method of claim 8 wherein from about 0.01 to about 30 parts by weight of said interparticle crosslinking agent per 100 parts by weight of said precursor particles is mixed with 0.01 to about 60 parts by weight of water and said hydrophilic organic solvent per 100 parts by weight of said precursor particles.

10. The method of claim 8 wherein step (d) comprises heating said interparticle crosslinking agent and said aggregates for a sufficient time at sufficient temperature to react said interparticle crosslinking agent with said aggregates to form crosslink bonds between said precursor particles to form interparticle crosslinked aggregates.

11. The method of claim 10 additionally comprising the step of:

(e) surface crosslinking the interparticle crosslinked aggregates.

12. The method of claim 1, 6, 10, or 11 wherein the polymeric composition has a mass average particle size at least about 50% greater than the mass average particle size of said precursor particles.

13. A method for producing a particulate, absorbent, polymeric composition comprising interparticle covalently crosslinked aggregates, the method comprising the steps of:

(a) providing substantially dry precursor particles of substantially water-insoluble, absorbent, hydrogel-forming, polymer material;

said polymer material consisting essentially of slightly network crosslinked products of partially neutralized polyacrylic acid;

(b) applying (i) an interparticle crosslinking agent and (ii) 0.01 to about 60 pads by weight per 100 parts by weight of said precursor particles of water, a hydrophilic organic solvent, or a mixture thereof onto said precursor particles;

provided that when water is applied to said precursor particles it is used in a proportion of from about 0.1 parts to about 10 parts by weight per 100 parts by weight of the precursor particles;

said interparticle crosslinking agent being selected from the group consisting of trimethylol propane, ethylene glycol, 1,2-propanediol, 1,3-propanediol, or glycerol;

(c) forming a multiplicity of aggregates of said precursor particles; and

(d) heating said interparticle crosslinking agent and said aggregates to react said interparticle crosslinking agent with said polymer material of said precursor particles of said aggregates, while insuring minimal dissociation forces or stresses are introduced during the reaction step, to form covalent crosslink bonds between said precursor particles to form interparticle crosslinked aggregates, said interparticle crosslinked aggregates being present in the polymeric composition in an amount such that the polymeric composition has a mass average particle size at least about 30% greater than the mass average particle size of said precursor particles.

14. The method of claim 13 wherein step (d) is carried out at a temperature in the range of from about 170°

C. to about 220°

C. for at least about 20 minutes.

15. The method of claim 14 wherein step (d) is carried out at a temperature of between about 170°

C. and about 220°

C. for between about 2 hours and about 20 minutes.

16. The method of claim 15 wherein step (d) is carried out at a temperature of between about 190°

C. and about 210°

C. for about 45 minutes to about 30 minutes.

17. The method of claim 15 wherein said interparticle crosslinking agent is coated on said precursor particles.

18. The method of claim 17 wherein said interparticle crosslinking agent is mixed with water, a hydrophilic organic solvent, or mixtures thereof.

19. The method of claim 18 wherein step (c) comprises

(i) coating an associating agent onto said precursor particles, and

(ii) physically contacting said precursor particles to form a multiplicity of aggregates.

20. The method of claim 18 wherein said associating agent is selected from the group consisting of water, a hydrophilic organic solvent, an interparticle crosslinking agent, or mixtures thereof.

21. The method of claim 20 additionally comprising the step of:

(e) surface crosslinking at least said interparticle crosslinked aggregates.

22. The method of claim 21 wherein said interparticle crosslinking agent is glycerol, and said hydrophilic organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, or mixtures thereof.

23. The method of claim 22 wherein said precursor particles are formed by an aqueous solution polymerization process.

24. The method of claim 13, 15, 18, 21, 22, or 23 wherein the polymeric composition has a mass average particle size at least about 50% greater than the mass average particle size of said precursor particles.