# US 10,865,276 B2 · Process for preparing an aqueous dispersion of polymeric microspheres

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,865,276 B2
- Document ID: US10865276B2
- Status: Granted
- Kind: B2
- Application number: 15/930,514
- Filed: 2020-05-13
- Published: 2020-09-10
- Granted: 2020-12-15
- Earliest claimed: 2017-09-05
- Assignees: Rohm and Haas Company
- Applicants: Rohm and Haas Company
- Inventors: James C. Bohling; Ibrahim Eryazici; Philip R. Harsh; Partha S. Majumdar; Edwin A. Nungesser
- Web page: https://patentgrep.com/patent/US10865276B2

## CPC

- C08F 12/24: Phenols or alcohols
- C08F 2/26: anionic
- C08F 4/40: Redox systems
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08F 285/00: Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
- C08G 65/22: Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08L 71/02: Polyalkylene oxides
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C09D 7/42: Gloss-reducing agents
- C09D 7/65: macromolecular (C09D7/41-C09D7/48 take precedence)
- C09D 7/70: {characterised by shape, e.g. fibres, flakes or microspheres}
- C08F 2438/02: Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
- C08L 2201/50: Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
- C08L 2201/54: Aqueous solutions or dispersions
- C08L 2312/00: Crosslinking
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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 composition comprising an aqueous dispersion of microspheres and a class of a nonionic polyalkylene oxide of a distyryl or tristyryl phenol or an anionic polyalkylene oxide salt of a distyryl or tristyryl phenol and a process for preparing the composition. The microspheres have an average particle size in the range of from 1 μm to 25 μm, as well as a low coefficient of variation and low gel concentration; the composition is useful in coatings applications, especially where a matte finish is desired.

## Claims

### Claim 1

A process comprising the step of contacting, under polymerization conditions and in the presence of a nonionic polyalkylene oxide of a distyryl or tristyryl phenol or an anionic polyalkylene oxide salt of a distyryl or tristyryl phenol, an aqueous dispersion of first microspheres comprising structural units of a first monoethylenically unsaturated nonionic monomer with a first stage monomer comprising from 70 to 100 weight percent of a second monoethylenically unsaturated nonionic monomer, based on the weight of first stage monomer, to grow out the first microspheres to form an aqueous dispersion of second microspheres, wherein the first microspheres have a particle size in the range of from 1 μm to 15 μm and the second microspheres have a particle size in the range of from 1.1 μm and 25 μm.

### Claim 2 (depends on 1)

The process of claim 1 wherein the first microspheres have a particle size in the range of from 2.5 μm to 12 μm, and the second microspheres have a particle size in the range of from 4.5 μm to 20 μm; and wherein the nonionic polyalkylene oxide of a distyryl or tristyryl phenol or anionic polyalkylene oxide salt of a distyryl or tristyryl phenol is represented by the compound of Formula I:
where each R is independently C1-C4-alkyl; R1 is H, 1-phenethyl-(R)p, CH2—CR═CH2, or CH═CHCH3; each R2 is independently H, allyl, methyl, acrylate, methacrylate, or —CH2CHR3OX; each R3 is independently H, methyl, or ethyl; m is 0 to 5; n is 6 to 40; p is 0, 1 or 2; and O—X is hydroxyl, methoxyl, a sulfate or a phosphate.

### Claim 3 (depends on 2)

The process of claim 2 wherein the compound of Formula I is represented by the compound of Formula II, Formula III, or Formula IV:
where n is from 10 to 20, X is —SO3H, —SO3Y, —H2PO3, —HPO3Y, or —PO3Y2, where Y is Li+, Na+, K+, or NH4+; or
where n is 12 to 18; or

### Claim 4 (depends on 3)

The process of claim 3 wherein the first microspheres have a particle size in the range of from 2.5 μm to 12 μm, and the second microspheres have a particle size in the range of from 4.5 μm to 20 μm; wherein the concentration of the nonionic polyalkylene oxide of a distyryl or tristyryl phenol or anionic polyalkylene oxide salt of a distyryl or tristyryl phenol is in the range of from 0.2 to 1 weight percent, based the weight of first stage monomers.

### Claim 5 (depends on 4)

The process of claim 4 wherein the aqueous dispersion of first microspheres is further contacted under polymerization with an additional first stage monomer which is a multiethylenically unsaturated nonionic monomer at a concentration in the range of from 0.1 to 15 weight percent, based on the weight of first stage monomers, wherein the second microspheres have a Tg of less than 25° C.

### Claim 6 (depends on 5)

The process of claim 5 wherein the second microspheres are further staged with a salt of the compound of Formula II or III and a second stage monoethylenically unsaturated nonionic monomer under polymerization conditions to form a dispersion of third microspheres with a domain having a Tg of less than 25° C., and a domain with a Tg of greater than 50° C.

### Claim 7 (depends on 1)

The process of claim 1 wherein the first microspheres are prepared by a) contacting an aqueous dispersion of an oligomeric seed with a monomer in the presence of a hydrophobic initiator to transport the initiator into the seed, and b) polymerizing the monomer; wherein the oligomer seed has a weight average molecular weight in the range of from 800 to 20,000 g/mol and an average diameter in the range of from 200 nm to 8000 nm.