# US 11,999,810 B2 · Process for producing an aqueous polymer dispersion

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- Number: US 11,999,810 B2
- Document ID: US11999810B2
- Status: Granted
- Kind: B2
- Application number: 17/257,969
- Filed: 2019-07-04
- Published: 2021-09-02
- Granted: 2024-06-04
- Earliest claimed: 2018-07-05
- Assignees: BASF SE; Universidad Del Pais Vasco/Euskal Herriko Unibertsitatea
- Applicants: BASF SE; Universidad del Paìs Vasco / Euskal Herriko Unibertsitatea
- Inventors: Massimo Bandiera; Roelof Balk; Bastiaan Lohmeijer; Maria Jesus Barandiaran
- Web page: https://patentgrep.com/patent/US11999810B2

## CPC

- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08F 2/22: Emulsion polymerisation
- C08J 3/07: from polymer solutions
- C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)}
- C09D 151/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence)}
- C08J 2351/00: Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)

## Abstract

The present invention relates to a process for producing an aqueous polymer dispersion of polymerized ethylenically unsaturated monomers, where the process has a first polymerization step as an aqueous radical emulsion polymerization of a first monomer composition M.a and a subsequent further polymerization step as an aqueous radical emulsion polymerization of a second monomer composition M.b, where the monomers M comprise at least one monomer M0 which is selected from compounds of formula 1, wherein X is Cl, Br or OS(O)2R3, Y is H, Cl, Br, OS(O)2R4, C1-C10-alkyl, or C(═O)OR5, R1 is H or C1-C10-alkyl, R2 is H or C1-C10-alkyl, R3 is C1-C10-alkyl, R4 is C1-C10-alkyl, R5 is C1-C20-alkyl. The invention also relates to an aqueous polymer dispersion obtainable by such a process as well as the use of such dispersions.

## Claims

### Claim 1

A process for producing an aqueous polymer dispersion of polymerized ethylenically unsaturated monomers M, where the monomers M comprise
a) at least one monomer M0 which is selected from compounds of formula 1,
wherein X is Cl, Br or OS(O)2R3,
Y is H, C1-C10-alkyl, Cl, Br, OS(O)2R4, or C(═O)OR5,
R1 is H or C1-C10-alkyl,
R2 is H or C1-C10-alkyl,
R3 is C1-C10-alkyl,
R4 is C1-C10-alkyl, and
R5 is C1-C20-alkyl;
b) at least one monomer M1 which is selected from nonionic monoethylenically unsaturated monomers having a solubility in deionized water of at most 60 g/L at 25° C. and 1 bar, and being different from monomers M0,
c) at least one monomer M2 which is selected from ethylenically unsaturated monomers having a carboxylic acid group,
d) optionally one or more ethylenically unsaturated monomers M3 that are different from monomers M0, M1, and M2,
where the process comprises
i) a first polymerization step of an aqueous radical emulsion polymerization of a first monomer composition M.a to prepare a polymer, wherein the first monomer composition M.a comprises: at least 0.1% by weight, based on the total weight of the monomer composition M.a, of at least one monomer M0, and
at least 1% by weight, based on the total weight of the monomer composition M.a, of at least one monomer M2,
ii) neutralizing at least 50% of the carboxylic acid groups derived from monomers M2 of the polymer of step i) by addition of a base, and subsequently
iii) at least one further polymerization step of an aqueous radical emulsion polymerization of a second monomer composition M.b in the presence of the polymer of step ii), where the monomers M comprise
a. 5 to 95 wt %, based on the total amount of the monomers M, of the monomer compositions M.a., and
b. 5 to 95 wt. %, based on the total amount of the monomers M, of the monomer composition M.b.

### Claim 2 (depends on 1)

The process according to claim 1, where the monomers M0 are selected from compounds of formula 1a,
wherein X, R1, R2 and R5 are as defined for formula 1.

### Claim 3 (depends on 2)

The process according to claim 2, where
R1 is H,
R2 is H or methyl,
R5 is C1-C10-alkyl,
X is Cl, Br.

### Claim 4 (depends on 1)

The process according to claim 1, where the monomer composition M.a comprises
a) 0.1 to 10% by weight, based on the total weight of monomer composition M.a, of at least one monomer M0,
b) 70 to 98.9% by weight, based on the total weight of monomer composition M.a, of at least one monomer M1,
c) 1 to 20% by weight, based on the total weight of the monomer composition M.a, of at least one monomer M2,
d) 0 to 20% by weight, based on the total weight of the monomer composition M.a, of at least one monomer M3.

### Claim 5 (depends on 1)

The process according to claim 1, where the monomer composition M.a comprises
0.5 to 9% by weight based on the total weight of the monomer composition M.a, of at least one monomer M0, and/or
3 to 19% by weight based on the total weight of the monomer composition M.a, of at least one monomer M2.

### Claim 6 (depends on 1)

The process according to claim 1, where the monomer composition M.b comprises
a) 90 to 100% by weight, based on the total weight of the monomer composition M.b, of at least one monomer M1,
b) 0 to 2% by weight, based on the total weight of the monomer composition M.b, of at least one monomer M2,
c) 0 to 10% by weight, based on the total weight of the monomer composition M.b, of at least one monomer M3.

### Claim 7 (depends on 1)

The process according to claim 1, where the monomer composition M.b consists of one or more monomers M1 or of a mixture of monomers M1 and M3.

### Claim 8 (depends on 1)

The process according to claim 1, where the monomers M1 are selected from the group consisting of C1-C20-alkyl esters of acrylic acid, C20-cycloalkyl esters of acrylic acid, C1-C20-alkylesters of methacrylic acid, C5-C20-cycloalkyl esters of methacrylic acid, and monovinyl aromatic monomers, and mixtures thereof.

### Claim 9 (depends on 1)

The process according to claim 1, where the monomers M2 are selected from the group consisting of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and mixtures thereof.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the monomers M3 are selected from the group consisting of
primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms (monomers M3.1),
N—C1-C10 alkyl amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms (monomers M3.2),
monoethylenically unsaturated monomers bearing a urea and/or a keto group (monomers M3.3),
hydroxyalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms (monomers M3.4),
monoethylenically unsaturated monomers which bear at least one mono-, di- and/or tri-C1-C4-alkoxysilane group (monomers M3.5),
multiethylenically unsaturated monomers (monomers M3.6),
monoethylenically unsaturated monomers having at least one acidic group and/or a salt thereof (monomers M3.7), with the proviso that they are different from monomers M2,
monoethylenically unsaturated monomers bearing at least one epoxy group,
and mixtures thereof.

### Claim 11 (depends on 1)

The process according to claim 1, where the base that is used in step ii) is a volatile base.

### Claim 12 (depends on 11)

The process according to claim 11, where the base that is selected from
ammonia,
primary, secondary, and tertiary amines,
and mixtures thereof.

### Claim 13 (depends on 1)

The process according to claim 1, where in step ii), the base is added in such an amount that a pH in the range of 5 to 10 results.

### Claim 14 (depends on 1)

The process according to claim 1, where an emulsifier E is present at the first polymerization step and/or at the second polymerization step.

### Claim 15 (depends on 1)

The process according to claim 1, where the weight average molecular weight Mw of the polymer obtained from the polymerization of step i) is in the range of 1000 to 50000 g/mol.

### Claim 16 (depends on 1)

The process according to claim 1, where the first polymerization step i) is performed in the presence of a chain transfer agent, which does not have any ethylenically unsaturated double bonds.

### Claim 17 (depends on 1)

An aqueous polymer dispersion obtained by the process according to claim 1.

### Claim 18 (depends on 17)

The aqueous polymer dispersion according to claim 17, where the polymer particles contained in the aqueous polymer dispersion have a polymer phase A formed by the monomer composition M.a and a polymer phase B formed by the monomer composition M.b, where the polymer phase A has a glass transition temperature Tg(A), and the polymer phase B has a glass transition temperature Tg(B), where the difference Tg(A)-Tg(B) is at least 10 K, where Tg(A) and Tg(B) are theoretical glass transition temperatures as determined by the Fox equation.

### Claim 19 (depends on 18)

The aqueous polymer dispersion according to claim 18,
wherein the glass transition temperature Tg(A) is in the range of 0 to 150° C. and/or
wherein the glass transition temperature Tg(B) is in the range of −50 to 120° C.

### Claim 20 (depends on 18)

The aqueous polymer dispersion according to claim 18, wherein the particle size distribution of these polymer particles has a maximum in the range of 20 to 300 nm.

### Claim 21 (depends on 17)

The aqueous polymer dispersion according to claim 17, wherein the aqueous polymer dispersion has a solids content of 35 to 55%.

### Claim 22 (depends on 17)

A water-borne coating composition containing the aqueous polymer dispersion according to claim 17,
which further contains at least a pigment and/or
which further contains at least a filler.

### Claim 23 (depends on 22)

A method of producing a coating on a surface comprising
(a) applying the water-borne coating composition according to claim 22 to the surface, and
(b) allowing the composition to dry to produce the coating.