# US 9,518,134 B2 · Water-absorbent surface-modified-clay linked polymers

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- Number: US 9,518,134 B2
- Document ID: US9518134B2
- Status: Granted
- Kind: B2
- Application number: 13/326,376
- Filed: 2011-12-15
- Published: 2012-06-21
- Granted: 2016-12-13
- Earliest claimed: 2010-12-15
- Assignees: The Procter & Gamble Company
- Applicants: Torsten Lindner; Axel Meyer; Michael Moeller; Josef Breu; Manuela Stirner
- Inventors: Torsten Lindner; Axel Meyer; Michael Moeller; Josef Breu; Manuela Stirner
- Web page: https://patentgrep.com/patent/US9518134B2

## CPC

- C08F 2/44: Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
- A61L 15/60: Liquid-swellable gel-forming materials, e.g. super-absorbents
- C09C 1/42: Clays
- A61L 15/18: containing inorganic materials
- C01P 2004/20: extending in two dimensions, e.g. plate-like
- C01P 2004/22: with a polygonal circumferential shape
- C01P 2004/54: Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
- C08J 2300/14: Water soluble or water swellable polymers, e.g. aqueous gels
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

An aqueous acidic polymerization liquid comprising polymerizable monomers or oligomers with carboxylate and/or carboxylic acid moiety or moieties, and basal surface modified clay that is homogenously dispersable in said liquid is provided, and also methods for making such liquids, and also surface-modified-clay linked water-absorbing polymers made with said liquids and methods, and disposable absorbent articles comprising such surface-modified-clay linked water-absorbing polycarboxylate/polycarboxylic acid polymers.

## Claims

### Claim 1

A water-absorbing surface-modified-clay linked polycarboxylic acid and/or polycarboxylate polymer, obtainable by a polymerization reaction comprising the steps of:
a) obtaining an aqueous polymerization reaction liquid, comprising (i) homogeneously dispersed therein, clay platelets with opposing basal platelet surfaces and platelet edges; and (ii) dissolved or homogeneously dispersed therein, polymerizable monomers comprising a carboxylic acid and/or carboxylate group, and/or polymerizable oligomers of one or more of the monomers;
wherein the aqueous liquid has a pH of about 6 or less; wherein at least about 20%, by weight, of the monomers and/or oligomers are neutralized; and wherein the basal surface(s) of the clay platelets are modified with a surface modification compound(s);
b) initiating the polymerization of the monomers and/or oligomers in the liquid of step a);
wherein the water-absorbing surface-modified clay linked polymer exhibits a Centrifuge Retention Capacity (CRC) in a 0.9% saline solution in demineralized water, of at least about 10 g of saline per gram of polymer.

### Claim 2

A method for making a water-absorbing surface-modified-clay linked polycarboxylic acid and/or polycarboxylate polymer, comprising the steps of:
a) obtaining an aqueous polymerization reaction liquid comprising i) homogeneously dispersed therein, clay platelets with opposing basal platelet surfaces and platelet edges; and ii) dissolved or homogeneously dispersed therein, polymerizable monomers comprising a carboxylic acid group and/or carboxylate group, and/or polymerizable oligomers of one or more of the monomers;
wherein the aqueous liquid has a pH of about 6 or less; wherein at least about 20%, by weight, of the monomers and/or oligomers are neutralized; and wherein the basal surface(s) of the clay platelets are modified with one or more surface modification compound(s);
b) obtaining a polymerization initiator system;
c) combining the liquid of a) with the polymerization initiator system of b) and polymerizing the monomers and/or oligomers;
wherein the water-absorbing surface-modified clay linked polymer exhibits a Centrifuge Retention Capacity (CRC) in a 0.9% saline solution in demineralized water, of at least about 10 g of saline per gram of polymer.

### Claim 3 (depends on 1)

A polymer as in claim 1, wherein at least about 20 mol % (based on all monomers and or oligomers) of the polymerizable monomers and/or of the polymerizable oligomers have a carboxylate group with cationic counter ion.

### Claim 4 (depends on 1)

A polymer as in claim 1, wherein the reaction liquid comprises monomers that are acrylic acid and/or acrylate salt, and the polymer is a polyacrylic acid and/or polyacrylate polymer.

### Claim 5 (depends on 1)

A polymer as in claim 1, wherein the one or more surface modification compound(s) has a cationic moiety capable of bonding to a clay platelet's basal plate.

### Claim 6 (depends on 5)

A polymer as in claim 5, wherein the one or more surface modification compound(s) also has an anionic moiety and/or one or more hydroxyl groups.

### Claim 7 (depends on 1)

A polymer as in claim 1, wherein the one or more surface modification compounds comprise a unsaturated moiety capable of covalently bonding to the polymerizable monomer or polymerizable oligomer, and/or the surface modification compound comprises a moiety capable of covalently or ionically bonding to the carboxy moiety of the monomer, oligomer or polymer.

### Claim 8 (depends on 1)

A polymer as in claim 1, wherein the one or more surface modification compound(s) are one or more compounds that sterically hinder the platelet surfaces, the compound having a length of at least about 10 angstroms (Å).

### Claim 9 (depends on 8)

A polymer as in claim 8, wherein the one or more surface modification compound(s) have at least one moiety comprising a carbon chain of at least 6 carbon atoms.

### Claim 10 (depends on 1)

A polymer as in claim 1, wherein the one or more surface modification compounds have one or more oligo-alkyleneoxide (AE) moieties.

### Claim 11 (depends on 10)

A polymer as in claim 10, wherein the one or more surface modification compounds have one or more oligo-ethyleneoxide moieties.

### Claim 12 (depends on 1)

A polymer as in claim 1, wherein the surface modification compound has one or more alkylated nitrogen moieties and/or alkoxylated nitrogen moieties.

### Claim 13 (depends on 1)

A polymer as in claim 1, wherein the one or more surface modification compounds include or are an oligo- or poly-ethyleneimine, an oligo- or poly-ethylene diamine, or ethylene diamine, or derivative of any of these, and mixtures thereof.

### Claim 14 (depends on 13)

A polymer as in claim 13, wherein the one or more surface modification compounds include or are hexamethylene diamine or ethylendiamine, or derivatives thereof, or a mixture thereof.

### Claim 15 (depends on 1)

A polymer as in claim 1, wherein the polymers are additionally crosslinked by organic crosslinking compounds, or wherein the polymerization reaction liquid comprises an organic crosslinking compound.

### Claim 16 (depends on 1)

A polymer as in claim 1, wherein the clay platelets have edge(s) that are modified by one or more edge-modification compound selected from the group consisting of:
i) phosphorylation compounds;
ii) silanization compounds of the formula SiRIRIIRIIIRIV, wherein the moieties RI, RII, RIII, RIV are each selected from the group consisting of the subgroups: a) Alkyl, Aryl, O-Alkyl(Alkoxy), N-Alkyls, Alkenes, alkenyls; and b) hydrogen, halide; and c) Hydroxy, Carboxy-containing moieties, Epoxy-containing moieties, Isocyano-containing moieties, provided that at least one and at the most three of the moieties are selected from the subgroup a) and that at least one and at the most three of the moieties are selected from the subgroup c) and that at the most one of the moieties is selected from the subgroup b);
iii) fluorination compounds; and
iv) mixtures of any of the above.

### Claim 17 (depends on 16)

A polymer as in claim 16, wherein the phosphorylation compounds are selected from the group consisting of: phosphate salts, condensed phosphate salts, derivatives thereof and acid forms thereof; phosponic acid, derivatives thereof and salts thereof, and combinations thereof.

### Claim 18 (depends on 16)

A polymer as in claim 16, wherein the fluorination compounds include an MF salt wherein M is a mono-valent counterion.

### Claim 19 (depends on 1)

A polymer as in claim 1, wherein the pH is from about 3 to about 5.

### Claim 20

A method for making an aqueous polymerization reaction liquid suitable for making water-absorbing surface-modified-clay linked polyacrylate/poly acrylic acid polymers, the method comprising the steps of:
a) obtaining a first aqueous mixture, being an aqueous solution or dispersion of the acrylic acid and/or acrylate salt monomers, or oligomers thereof, wherein at least about 20%, by weight, of the monomers or oligomers are neutralized;
b) obtaining a clay or clay dispersion; and
c) obtaining one or more surface modification compound(s) having a cationic moiety that can bind to a clay platelet's basal plate, or a dispersion or solution thereof,
d) (i) combining the solution or dispersion of (a) and the clay or clay dispersion of (b) first, and then combining this mixture with the surface modification compound or dispersion or solution of (c); or
(ii) combining the solution or dispersion of (a) and the clay or clay dispersion of (b) and the surface modification compound or dispersion or solution of (c) simultaneously; or
(iii) combining the clay or clay dispersion of (b) and the surface modification compound or dispersion or solution of (c) first, and then combining this with the solution or dispersion of (a); and
e) ultrasonic or shear force mixing at least in step d)(i), d)(ii), or d(iii);
to obtain the aqueous polymerization reaction liquid, which has a pH of about 6 or less, which comprises the polymerizable monomers, polymerizable oligomers and/or mixtures thereof, and which has homogeneously dispersed therein clay platelets with modified basal surfaces;
wherein the water-absorbing surface-modified clay linked polymer exhibits a Centrifuge Retention Capacity (CRC) in a 0.9% saline solution in demineralized water, of at least about 10 g of saline per gram of polymer.

### Claim 21 (depends on 20)

A reaction liquid, obtainable by the method of claim 20, comprising: (i) homogeneously dispersed therein, clay platelets with opposing basal platelet surfaces and platelet edges; and (ii) dissolved or homogeneously dispersed therein, acrylic acid monomers and/or acrylate salt monomers, and/or polymerizable oligomers of one or more of the monomers; wherein the aqueous liquid has a pH of about 6 or less; and wherein the clay platelet's basal surface(s) are modified with a surface modification compound(s), having a cationic moiety capable of bonding to a clay platelet's basal plate.

### Claim 22 (depends on 1)

A disposable absorbent article comprising a polymer according to claim 1.

### Claim 23 (depends on 22)

A disposable absorbent article as in claim 22, wherein the absorbent article is selected from the group consisting of diapers, training pants, adult incontinence diapers, adult incontinence pants, adult incontinence pads, diaper liners, diaper inserts, sanitary napkins, panty-liners, and tampons.

### Claim 24 (depends on 2)

A disposable absorbent article comprising a polymer made according to the method of claim 2.

### Claim 25 (depends on 24)

A disposable absorbent article as in claim 24, wherein the absorbent article is selected from the group consisting of diapers, training pants, adult incontinence diapers, adult incontinence pants, adult incontinence pads, diaper liners, diaper inserts, sanitary napkins, panty-liners, and tampons.