# US 5,710,207 A · Block polymers containing ester groups as defoamers for aqueous systems

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- Number: US 5,710,207 A
- Document ID: US5710207A
- Status: Granted
- Kind: A
- Application number: 08/615,235
- Filed: 1996-04-10
- Granted: 1998-01-20
- Earliest claimed: 1993-09-15
- Assignees: Henkel Kommanditgesellschaft auf Aktien
- Inventors: Thomas Moller; Ulrich Eicken; Herbert Fischer; Horst-W. Wollenweber; Wolfgang Gress; Christian de Haut; Ulrike Mahler; Manfred Gorzinski; Hans-Jurgen Sladek
- Web page: https://patentgrep.com/patent/US5710207A

## CPC

- D06P 1/6136: {Condensation products of esters, acids, oils, oxyacids with oxiranes}
- B01D 19/0404: {characterised by the nature of the chemical substance}
- C08G 63/664: derived from hydroxy carboxylic acids
- C09D 5/024: {characterised by the additives}
- C11D 3/0026: {Low foaming or foam regulating compositions}
- C11D 3/3715: {Polyesters or polycarbonates}
- D06M 15/53: Polyethers (polyacetals D06M15/39)
- Y10T 428/2993: Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T 428/2998: including synthetic resin or polymer
- D06P: DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method of using compositions as foam regulators for water-based systems with a tendency to foam is provided. The method employs a block copolymer containing ester groups corresponding to general formula (I): A--(CH.sub.2 CH.sub.2 O).sub.n --B (I) in which n is an integer of 4 to 300, A is an optionally polymeric hydroxycarboxylic acid function and B is hydrogen, an alkyl or alkenyl radical containing 1 to 22 carbon atoms, a phenyl or benzyl radical or has the same meaning as A. Also provided is a granular free-flowing foam regulating formulation which contains 0.5% by weight to 30% by weight of the block copolymer containing ester groups adsorbed onto from 70% by weight to 99.5% by weight of a granular, substantially inorganic phosphate-free support material.

## Claims

### Claim 1

A method of regulating the foaming of water-based systems with a tendency to foam, said method comprising adding to a water-based system with a tendency to foam a block copolymer containing ester groups, said block copolymer corresponding to the general formula (I):
A--(CH.sub.2 CH.sub.2 O).sub.n --B (I)
in which n is an integer of 4 to 300, A is a hydroxycarboxylic acid residue and B is hydrogen, an alkyl or alkenyl radical containing 1 to 22 carbon atoms, a phenyl or benzyl radical or has the same meaning as A.

### Claim 2 (depends on 1)

A method as claimed in claim 1 wherein in formula I, A is R.sup.1 (--O--R--CO).sub.a and B is (O--OC--R).sub.b --OR.sup.2, R is a linear or branched alkylene or alkenylene radical containing 1 to 43 carbon atoms, "a" is a number of 1 to 550, "b" is a number of 0 to 550 and R.sup.1 and R.sup.2 independently of one another represent hydrogen or an acyl group R.sup.3 CO--, where R.sup.3 is hydrogen or an alkyl or alkenyl radical containing 1 to 21 carbon atoms.

### Claim 3 (depends on 2)

A method as claimed in claim 2 wherein said block copolymer is a compound corresponding to formula (II), in which "n" is a number of 6 to 100, R is a linear or branched alkylene or alkenylene radical containing 2 to 18 carbon atoms, "a" is a number of 2 to 170, "b" is a number of 1 to 170, and R.sup.1 and R.sup.2 represent hydrogen.

### Claim 4 (depends on 1)

A method as claimed in claim 1 wherein said block copolymer contains units from a member selected from the group consisting of ricinoleic acid, 12-hydroxystearic acid, and mixtures thereof.

### Claim 5 (depends on 1)

A method as claimed in claim 1 wherein the water-containing system with a tendency to foam occurs in the production or further processing of foods or in fermentation processes.

### Claim 6 (depends on 1)

A method as claimed in claim 1 wherein the water-containing system with a tendency to foam occurs in the production or further processing of paints, lacquers or plastics.

### Claim 7 (depends on 1)

A method as claimed in claim 1 wherein the water-containing system with a tendency to foam is a surfactant-containing wash liquor or cleaning solution.

### Claim 8 (depends on 1)

A method as claimed in claim 1 wherein the water-containing system with a tendency to foam is a water-containing textile dyeing or pretreatment bath.

### Claim 9

A method of regulating the foaming of water-based systems with a tendency to foam, said method comprising adding to a water-based system with a tendency to foam a block copolymer containing ester groups, said block copolymer corresponding to the general formula (II):
R.sup.1 (--O--R--CO).sub.a --(OCH.sub.2 CH.sub.2).sub.n --(O--OC--R).sub.b --OR.sup.2 (II)
in which "n" is a number of 6 to 100, R is a linear or branched alkylene or alkenylene radical containing 2 to 18 carbon atoms, "a" is a number of 2 to 170, "b" is a number of 1 to 170 and R.sup.1 and R.sup.2 represent hydrogen.

### Claim 10 (depends on 9)

A method as claimed in claim 9 wherein R is derived from a member selected from the group consisting of ricinoleic acid, 12-hydroxystearic acid, and mixtures thereof.

### Claim 11

A granular free-flowing foam regulating formulation comprising 0.5% by weight to 30% by weight of a block copolymer containing ester groups, said block copolymer corresponding to the general formula (I):
A--(CH.sub.2 CH.sub.2 O).sub.n --B (I)
in which n is an integer of 4 to 300, A is a hydroxycarboxylic acid residue and B is hydrogen, an alkyl or alkenyl radical containing 1 to 22 carbon atoms, a phenyl or benzyl radical or has the same meaning as A, said block copolymer being adsorbed onto 70% by weight to 99.5% by weight of a granular, substantially inorganic phosphate-free support material.

### Claim 12 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said formulation contains 1% by weight to 25% by weight of said block copolymer and 75% by weight to 99% by weight of said support material.

### Claim 13 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said formulation contains 2% by weight to 12% by weight of said block copolymer and 88% by weight to 98% by weight of said support material.

### Claim 14 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said support material is further comprised of a member selected from the group consisting of alkalis, detergent builders, layered silicate, a bleaching agent, and mixtures of two or more of said members.

### Claim 15 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said support material is further comprised of a member selected from the group consisting of alkali metal carbonate, alkali metal silicate, alumosilicate, bentonite, alkali metal perborate, alkali metal percarbonate, and mixtures of two or more of said members.

### Claim 16 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein in formula I, A is R.sup.1 (--O--R--CO).sub.a and B is (O--OC--R).sub.b --OR.sup.2, R is a linear or branched alkylene or alkenylene radical containing 1 to 43 carbon atoms, "a" is a number of 1 to 550, "b" is a number of 0 to 550 and R.sup.1 and R.sup.2 independently of one another represent hydrogen or an acyl group R.sup.3 CO--, where R.sup.3 is hydrogen or an alkyl or alkenyl radical containing 1 to 21 carbon atoms.

### Claim 17 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said block copolymer is a compound corresponding to formula (II), in which "n" is a number of 6 to 100, R is a linear or branched alkylene or alkenylene radical containing 2 to 18 carbon atoms, "a" is a number of 2 to 170, "b" is a number of 1 to 170, and R.sup.1 and R.sup.2 represent hydrogen.

### Claim 18 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said block copolymer contains units from a member selected from the group consisting of ricinoleic acid, 12-hydroxystearic acid, and mixtures thereof.

### Claim 19 (depends on 11)

A foam regulating formulation as claimed in claim 11 wherein said formulation further comprises a surfactant in an amount of no more than 10% by weight of said formulation.

### Claim 20 (depends on 19)

A foam regulating formulation as claimed in claim 19 wherein said surfactant is present in an amount of from 0.5% to 3.5% by weight of said formulation.

### Claim 21 (depends on 19)

A foam regulating formulation as claimed in claim 19 wherein said surfactant is present in an amount of up to 30% by weight of said block copolymer.

### Claim 22 (depends on 19)

A foam regulating formulation as claimed in claim 19 wherein said surfactant is present in an amount of 5% to 10% by weight of said block copolymer.

### Claim 23 (depends on 19)

A foam regulating formulation as claimed in claim 19 wherein said surfactant is selected from the group consisting of alkylbenzenesulfonates and alkyl sulfates.

### Claim 24

A granular free-flowing foam regulating formulation comprising 2% by weight to 12% by weight of a block copolymer containing ester groups, said block copolymer corresponding to the general formula (II):
R.sup.1 (--O--R--CO).sub.a --(OCH.sub.2 CH.sub.2).sub.n --(O--OC--R).sub.b --OR.sup.2 (II)
in which "n" is a number of 6 to 100, R is a linear or branched alkylene or alkenylene radical containing 2 to 18 carbon atoms, "a" is a number of 2 to 170, "b" is a number of 1 to 170 and R.sup.1 and R.sup.2 represent hydrogen, said block copolymer being adsorbed onto 88% by weight to 98% by weight of a granular, substantially inorganic phosphate-free support material.

### Claim 25 (depends on 24)

A foam regulating formulation as claimed in claim 24 wherein R is derived from a member selected from the group consisting of ricinoleic acid, 12-hydroxystearic acid, and mixtures thereof.

### Claim 26 (depends on 24)

A foam regulating formulation as claimed in claim 24 further comprising a surfactant selected from the group consisting of alkylbenzenesulfonates and alkyl sulfates in an amount of from 5% to 10% by weight of said block copolymer.

### Claim 27 (depends on 11)

A process for the production of the granular foam regulating formulation claimed in claim 11 wherein said block copolymer is applied to the granular support material kept in motion.

### Claim 28 (depends on 27)

A process as claimed in claim 27 wherein said block copolymer is applied to the granular support material at a temperature above room temperature.

### Claim 29 (depends on 27)

A process as claimed in claim 27 wherein an aqueous suspension or dispersion of the block copolymer is used.

### Claim 30 (depends on 29)

A process as claimed in claim 29 wherein a dispersion aid is used.

### Claim 31 (depends on 29)

A process as claimed in claim 29 further comprising subjecting the foam regulating formulation to a subsequent drying step.

### Claim 32 (depends on 27)

A process as claimed in claim 27 wherein said block copolymer is dispersed in an aqueous solution or slurry of the support material and the dispersion is spray-dried.

### Claim 33 (depends on 32)

A process as claimed in claim 32 wherein said aqueous solution or dispersion is further comprised of a water-soluble or water-swellable polymer as a dispersion aid.