# US 11,306,170 B2 · Water-soluble and/or water-swellable hybrid polymer

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- Number: US 11,306,170 B2
- Document ID: US11306170B2
- Status: Granted
- Kind: B2
- Application number: 16/470,133
- Filed: 2017-12-06
- Published: 2020-01-16
- Granted: 2022-04-19
- Earliest claimed: 2016-12-15
- Assignees: Clariant International Ltd.
- Applicants: Clariant International Ltd.
- Inventors: Dirk Fischer; Katharina Berz; Gundula Starkulla
- Web page: https://patentgrep.com/patent/US11306170B2

## CPC

- C08L 5/00: Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- A61K 8/736: {Chitin; Chitosan; Derivatives thereof}
- A61K 8/737: {Galactomannans, e.g. guar; Derivatives thereof}
- A61K 8/8158: {Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers}
- A61Q 19/00: Preparations for care of the skin
- C08B 37/003: {Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof}
- C08B 37/0033: {Xanthan, i.e. D-glucose, D-mannose and D-glucuronic acid units, saubstituted with acetate and pyruvate, with a main chain of (beta-1,4)-D-glucose units; Derivatives thereof}
- C08B 37/0042: {Carragenan or carragen, i.e. D-galactose and 3,6-anhydro-D-galactose, both partially sulfated, e.g. from red algae Chondrus crispus or Gigantia stellata; kappa-Carragenan; iota-Carragenan; lambda-Carragenan; Derivatives thereof}
- C08B 37/0084: {Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates}
- C08B 37/0096: {Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof}
- C08F 2/14: Organic medium
- C08F 220/585: {and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]}
- C08F 251/00: Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08L 5/04: Alginic acid; Derivatives thereof
- C08L 5/08: Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
- C08L 5/12: {Agar or} agar-agar {, i.e. mixture of agarose and agaropectin}; Derivatives thereof
- C08L 33/04: Homopolymers or copolymers of esters {(C08L43/04 takes precedence)}
- C08L 33/26: Homopolymers or copolymers of acrylamide or methacrylamide
- A61K 2800/48: Thickener, Thickening system
- A61K 2800/5424: anionic
- A61K 2800/546: Swellable particulate polymers
- C08L 2312/00: Crosslinking
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A water-soluble and/or water-swellable hybrid polymer comprising: (i) from 5 wt.-% to 95 wt.-% water-soluble and/or water-swellable polysaccharide polymer; (ii) from 5 wt.-% to 95 wt.-% synthetic polymer comprising: (a) from 40 mol-% to 99.9 mol-% repeating units according to Formula (1) (b) from 0.01 mol-% to 5 mol-% crosslinking or branching units, wherein the crosslinking or branching units result from the incorporation of a monomer comprising at least two olefinically unsaturated double bonds; (c) from 0.01 mol-% to 88.51 mol-% of neutral structural units; (d) from 1.98 mol-% to 20 mol-% of anionic structural units, wherein the repeating anionic structural units result from the incorporation of a monomer comprising at least one carboxylate anion, and wherein the repeating anionic structural units are different from units (a); wherein components (i) and (ii) are polymerized by radical precipitation polymerization in a polar solvent.

## Claims

### Claim 1

A water-soluble and/or water-swellable hybrid polymer comprising:
(i) from 5 wt.-% to 95 wt.-% water-soluble and/or water-swellable polysaccharide polymer;
(ii) from 5 wt.-% to 95 wt.-% synthetic polymer comprising:
(a) from 40 mol-% to 99.9 mol-% repeating units according to Formula (1)
wherein:
R1 and R2 are independently selected from the group consisting of H, methyl or ethyl; A is a linear or branched C1-C12-alkyl group; and Q+is H+, NH4+ organic ammonium ions [NHR5R6R7]+ wherein R5, R6, and R7 independently of one another may be hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, singularly or multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a C6-C22alkylamidopropyl group, a linear mono-hydroxyalkyl group having 2 to carbon atoms or a linear or branched dihydroxyalkyl group having 3 to carbon atoms, and where at least one of the radicals R5, R6, and R7 is not hydrogen, or Q+is Li+, Na+, K+, ½ Ca++, ½ Mg++, ½ Zn++, ⅓ Al+++, or mixtures thereof;
(b) from 0.01 mol-% to 5 mol % crosslinking or branching units, wherein the crosslinking or branching units result from the incorporation of a monomer comprising at least two olefinically unsaturated double bonds;
(c) from 0.01 mol-% to 88.51 mol-% of neutral structural units;
(d) from 1.98 mol-% to 20 mol-% of anionic structural units, wherein the repeating anionic structural units result from the incorporation of a monomer comprising at least one carboxylate anion, and wherein the repeating anionic structural units are different from units (a);
wherein components (i) and (ii) are polymerized by radical precipitation polymerization in a polar solvent.

### Claim 2 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the monomers resulting in units (a), (b), (c) and/or (d) are/is neutralized with a base prior to the polymerization, and/or the hybrid polymer after polymerization is neutralized with a base.

### Claim 3 (depends on 2)

The water-soluble and/or water-swellable hybrid polymer according to claim 2, wherein the base is selected from bases comprising an ion selected from the group consisting of Li+, Na+, K+, Ca++, Mg++, Zn++, Al+++, and combinations thereof.

### Claim 4 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the repeating units according to Formula (1) result from the incorporation of a monomer selected from the group consisting of acryloyldimethyltaurates, acryloyl-1,1-dimethyl-2-methyltaurates, acryloyltaurates, acryloyl-N-methyltaurates, and combinations thereof.

### Claim 5 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the crosslinking or branching units result from the incorporation of a monomer according to Formula (2)
wherein,
R1 is independently selected from the group consisting of H, methyl or ethyl; and R2 is a linear or branched alkyl group having 1 to 6 carbon atoms, or is a linear or branched, mono- or polyunsaturated alkylene group having 2 to 6 carbon atoms.

### Claim 6 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the crosslinking or branching units result from the incorporation of a monomer according to Formula (3)
wherein,
R1 is independently selected from the group consisting of H, methyl or ethyl; and R2 is a linear or branched alkyl group having 1 to 6 carbon atoms, or is a linear or branched, mono- or polyunsaturated alkylene group having 2 to 6 carbon atoms; D, E, and F are independently methyleneoxy (—CH2O), ethyleneoxy (—CH2—CH2—O—), propyleneoxy (—CH(CH3)—CH2—O—), a linear or branched alkylene group having 1 to 6 carbon atoms, a linear or branched, singularly or multiply unsaturated alkenylene group having 2 to 6 carbon atoms, a linear mono-hydroxyalkylene group having 2 to 6 carbon atoms or a linear or branched dihydroxyalkylene group having 3 to 6 carbon atoms; and o, p, and q each independently are an integer from 1 to 50.

### Claim 7 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the hybrid polymer comprises at least 30 wt.-% polysaccharide polymer, by total weight of the hybrid polymer.

### Claim 8 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the crosslinking or branching units result from the incorporation of a crosslinker selected from the group consisting of methylenebisacrylamide; methylenebismethacrylamide; esters of unsaturated monocarboxylic and polycarboxylic acids with polyols, allyl compounds, allyl esters of phosphoric acid; and vinylphosphonic acid derivatives.

### Claim 9 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the polysaccharide polymer is selected from the group consisting of xanthan gum, carrageenan, guar gum, chitosan and alginate.

### Claim 10 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the polysaccharide polymer comprises glucose and/or galactose units.

### Claim 11 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the structure of the hybrid polymer is such that the polysaccharide polymer is a backbone onto which the synthetic polymer is grafted.

### Claim 12 (depends on 1)

The water-soluble and/or water-swellable hybrid polymer according to claim 1, wherein the radical precipitation polymerization is carried out in a polar solvent mixture comprising: I) water and II) a further compound.

### Claim 13 (depends on 1)

A composition comprising:
(i) at least one water-soluble and/or water-swellable hybrid polymer according to claim 1 and
(ii) at least one carrier.

### Claim 14 (depends on 13)

The composition according to claim 13, wherein the composition is selected from the group consisting of shampoo, body wash, facial cleanser, face mask, bubble bath, intimate wash, bath oil, cleansing milk, micellar water, make-up remover, cleansing wipes, hair mask, perfume, liquid soap, shaving soap, shaving foam, cleansing foam, day cream, anti-ageing cream, body milk, body lotion, body mousse, face serum, eye cream, sunscreen lotion, sun cream, face cream, after-shave lotion, pre-shaving cream, depilatory cream, skin-whitening gel, self-tanning cream, anti-acne gel, mascara, foundation, primer, concealer, blush, bronzer, blemish balm (bb) cream, eyeliner, night cream, eye brow gel, highlighter, lip stain, hand sanitizer, hair oil, nail varnish remover, conditioner, hair styling gel, hair styling cream, anti-frizz serum, scalp treatment, hair colorant, split end fluid, deodorant, antiperspirant, baby cream, insect repellent, hand cream, sunscreen gel, foot cream, exfoliator, body scrub, cellulite treatment, bar soap, cuticle cream, lip balm, hair treatment, eye shadow, bath additive, body mist, eau de toilette, mouthwash, toothpaste, lubricating gel, moisturizer, serum, toner, aqua sorbet, cream gel, styling mousse, dry shampoo, lip stick, lip gloss, hydro-alcoholic gel, body oil, shower milk, illuminator, lip crayon, hair spray, combing cream, and sunblock.

### Claim 15 (depends on 1)

A thickening agent, a structurant, and/or a rheology modifier comprising at least one water-soluble and/or water-swellable hybrid polymer according to claim 1.

### Claim 16

A process for thickening, adding structure to, and/or modifying a rheology of a composition comprising the step of adding at least one water-soluble and/or water-swellable hybrid polymer comprising:
(i) from 5 wt.-% to 95 wt.-% water-soluble and/or water-swellable polysaccharide polymer;
(ii) from 5 wt.-% to 95 wt.-% synthetic polymer comprising:
(a) from 40 mol-% to 99.9 mol-% repeating units according to Formula (1)
wherein:
R1 and R2 are independently selected from the group consisting of H, methyl or ethyl; A is a linear or branched C1-C12-alkyl group; and Q+is H+, NH4+ organic ammonium ions [NHR5R6R7]+ wherein R5, R6, and R7 independently of one another may be hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, singularly or multiply unsaturated alkenyl group having 2 to 22 carbon atoms, a C6-C22alkylamidopropyl group, a linear mono-hydroxyalkyl group having 2 to carbon atoms or a linear or branched dihydroxyalkyl group having 3 to carbon atoms, and where at least one of the radicals R5, R6, and R7 is not hydrogen, or Q+is Li+, Na+, K+, ½ Ca++, ½ Mg++, ½ Zn++, ⅓ +++, or mixtures thereof;
(b) from 0.01 mol-% to 5 mol-% crosslinking or branching units, wherein the crosslinking or branching units result from the incorporation of a monomer comprising at least two olefinically unsaturated double bonds;
(c) from 0.01 mol-% to 88.51 mol-% of neutral structural units;
(d) from 1.98 mol-% to 20 mol-% of anionic structural units, wherein the repeating anionic structural units result from the incorporation of a monomer comprising at least one carboxylate anion, and wherein the repeating anionic structural units are different from units (a);
wherein components (i) and (ii) are polymerized by radical precipitation polymerization in a polar solvent.