# US 10,308,730 B2 · Preparation of a redox initiated bimorphological latex

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- Number: US 10,308,730 B2
- Document ID: US10308730B2
- Status: Granted
- Kind: B2
- Application number: 15/703,346
- Filed: 2017-09-13
- Published: 2018-03-22
- Granted: 2019-06-04
- Earliest claimed: 2016-09-22
- Assignees: Rohm and Haas Company
- Applicants: Rohm and Haas Company
- Inventors: James C. Bohling; Arnold S. Brownell; Wei Gao
- Web page: https://patentgrep.com/patent/US10308730B2

## CPC

- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08F 2/001: {Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence)}
- C08F 2/24: with the aid of emulsifying agents
- C08F 212/36: Divinylbenzene
- C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 230/02: containing phosphorus
- C08F 285/00: Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
- C08K 3/22: of metals
- C08L 33/02: Homopolymers or copolymers of acids; Metal or ammonium salts thereof
- C08L 33/04: Homopolymers or copolymers of esters {(C08L43/04 takes precedence)}
- 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 143/02: Homopolymers or copolymers of monomers containing phosphorus
- C08K 2003/2241: {Titanium dioxide}
- C08L 43/02: Homopolymers or copolymers of monomers containing phosphorus
- C08L 2201/54: Aqueous solutions or dispersions
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2207/53: Core-shell polymer
- C09D 7/67: {Particle size smaller than 100 nm}
- C09D 7/68: {Particle size between 100-1000 nm}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- 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 an in situ preparation of a redox initiated bimorphological aqueous dispersion of first polymer particles with protuberating phosphorus acid cores and second polymer particles without protuberating cores. The method provides a more efficient way of making compositions for pigmented coating formulations.

## Claims

### Claim 1

An in situ method for preparing a redox initiated bimorphological aqueous dispersion of polymer particles comprising the steps of:
a) mixing together an aqueous dispersion of phosphorus acid-functionalized acrylic-based first seed polymer particles having a volume average particle size in the range of from 40 nm to 85 nm with an aqueous dispersion of acrylic-based second seed polymer particles comprising less than 1 weight percent structural units of a phosphorus acid monomer, based on the weight of the second seed polymer particles and having a volume average particle size in the range of from 20 nm to 80 nm;
b) contacting monomers with the aqueous dispersions of the first and second seed polymer particles under redox initiated emulsion polymerization conditions to form a dispersion of 1) polymer particles with a protuberating phosphorus acid functionalized core; and 2) polymer particles without a protuberating core; and wherein the weight-to-weight ratio of particles with the protuberating phosphorus acid functionalized core to particles without a protuberating core is in the range of 25:75 to 75:25.

### Claim 2 (depends on 1)

The method of claim 1 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles comprise structural units of: a) methyl methacrylate or styrene or a combination thereof; b) one or more acrylate monomers selected from the group consisting of ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate; and
c) phosphoethyl methacrylate; and wherein the monomers comprise: a) methyl methacrylate or styrene or a combination thereof; b) one or more acrylate monomers selected from the group consisting of ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate; and
c) less than 1 weight percent of a phosphorus acid monomer.

### Claim 3 (depends on 2)

The method of claim 2 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles further comprise: d) structural units of a carboxylic acid monomer or a salt thereof; and e) structural units of a multiethylenically unsaturated monomer.

### Claim 4 (depends on 2)

The method of claim 2 wherein the monomers further comprises a carboxylic acid monomer or a sulfur acid monomer or a salt thereof or a combination thereof.

### Claim 5 (depends on 4)

The method of claim 4 wherein the phosphorus acid-functionalized acrylic-based first seed polymer particles comprise, based on the weight of the first seed polymer particles: a) 3 to 8 weight percent structural units of phosphoethyl methacrylate or a salt thereof; b) from 1 to 5 weight percent structural units of acrylic acid or methacrylic acid or a salt thereof; c) from 0.2 to 5 weight percent structural units of a multiethylenically unsaturated monomer; d) from 50 to 65 weight percent structural units of butyl acrylate; and e) 25 to 45 weight percent structural units of methyl methacrylate; and wherein the monomers are added as a monomer emulsion and comprise, based on the weight of the monomers: a) from 40 to 60 weight percent of a first monomer selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate; b) 40 to 60 weight percent a second monomer selected from the group consisting of methyl methacrylate and styrene; c) from 0.1 to 5 weight percent of an acid monomer or a salt thereof, wherein the acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, 4-vinylbenzenesulfonic acid, and 2-acrylamido-2-methyl propanesulfonic acid; and d) less than 0.5 weight percent of a phosphorus acid monomer.

### Claim 6 (depends on 5)

The method of claim 5 wherein the monomers have the same monomer profile as the second seed polymer particles.

### Claim 7 (depends on 1)

The method of claim 1 wherein the aqueous dispersions of the first and second seed polymer particles are mixed together at a first-to-second seed polymer particles weight-to-weight ratio of from 1:2 to 10:1, wherein the monomer emulsion comprises less than 0.1 weight of a phosphorus acid monomer based on the weight of the monomer emulsion.

### Claim 8 (depends on 7)

The method of claim 7 wherein the ratio of volume average particle size of the protuberating core polymer particles to the non-protuberating core polymer particles is from 3:1 to 0.9:1.

### Claim 9 (depends on 8)

The method of claim 8 wherein the volume average particle size of the protuberating core polymer particles is in the range of from 110 to 160 nm, and the volume average particle size of the non-protuberating core polymer particles is in the range of from 40 to 130 nm.

### Claim 10 (depends on 9)

The method of claim 9 wherein weight-to-weight ratio of particles with the protuberating phosphorus acid functionalized core to particles without a protuberating core is in the range of 40:60 to 60:40.

### Claim 11 (depends on 1)

The method of claim 1 which comprises the further step of combining the bimorphological aqueous dispersion of polymer particles with TiO2 particles to form a dispersion of polymer particles that are adsorbed and not adsorbed to TiO2.

### Claim 12 (depends on 1)

The method of claim 1 wherein in step (b) from 1 to 10 weight percent of the monomer emulsion is polymerized under redox initiated emulsion polymerization conditions to form an aqueous dispersion of the second seed polymer particles, wherein the redox emulsion polymerization conditions comprise a) isoascorbic acid and t-amyl hydroperoxide as a redox pair;
and b) less than 0.1 weight percent of a persulfate initiator.