# US 2016/0355698 A1 · Multistage polymers and compositions thereof

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- Number: US 2016/0355698 A1
- Document ID: US20160355698A1
- Status: Published application
- Kind: A1
- Application number: 15/103,963
- Filed: 2014-12-03
- Published: 2016-12-08
- Earliest claimed: 2013-12-13
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Paul J. Harris; Michael J. Drewery; Eric Casebolt; Nicholas Foley
- Web page: https://patentgrep.com/patent/US20160355698A1

## CPC

- C09D 151/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence)}
- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C08K 5/523: with hydroxyaryl compounds
- C09D 151/06: grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
- 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)
- 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)

## Abstract

Provided are multistage polymers that comprise (i) a first stage comprising a first copolymer having a first theoretical Tg, the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and (ii) a second stage comprising a second polymer having a second theoretical Tg, the second polymer being derived from one or more hard ethylenically-unsaturated monomers. The multistage polymers can be in the form of multilayer particles that comprise (i) a first layer comprising the first copolymer; and (ii) a second layer surrounding at least a portion of the first layer comprising the second polymer. Also provided are aqueous compositions including one or more of the multistage polymers (or multilayer particles) described herein, as well as methods for making the multistage polymers (or multilayer particles) described herein.

## Claims

### Claim 1

An aqueous composition comprising an aryl phosphate surfactant and a multistage polymer, wherein the multistage polymer comprises
(i) a first stage comprising a first copolymer having a first theoretical glass transition temperature (Tg), the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and
(ii) a second stage comprising a second polymer having a second theoretical Tg, the second polymer being derived from one or more hard ethylenically-unsaturated monomers.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate.

### Claim 3

A multilayer particle comprising
(i) a first layer comprising a first copolymer having a first theoretical glass transition temperature (Tg), the first copolymer being derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and
(ii) a second layer surrounding at least a portion of the first layer comprising a second polymer having a second theoretical Tg, the second polymer being derived from at least 50% by weight of one or more hard ethylenically-unsaturated monomers, based on the total weight of monomers used to form the second polymer;
wherein the second theoretical Tg is at least 40° C. greater than the first theoretical Tg.

### Claim 4 (depends on 3)

The particle of claim 3, wherein the multistage particle exhibits a single Tg, measured using differential scanning calorimetry (DSC), ranging from −10° C. to 25° C.

### Claim 5

A multilayer particle comprising
(i) a first layer comprising a first copolymer derived from a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer; and
(ii) a second layer surrounding at least a portion of the first layer comprising a second polymer derived from at least 90% by weight of one or more hard ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof, based on the total weight of monomers used to form the second polymer;
wherein the particle exhibits a single Tg, measured using DSC, ranging from −10° C. to 25° C.

### Claim 6 (depends on 3)

The particle of claim 3,
wherein the first theoretical Tg of the first copolymer is 30° C. or less.

### Claim 7 (depends on 3)

The particle of claim 3,
wherein the second theoretical Tg of the second copolymer is at least 60° C.

### Claim 8 (depends on 3)

The particle of claim 3,
wherein the second theoretical Tg is at least 50° C. greater than the first theoretical Tg.

### Claim 9 (depends on 3)

The particle of claim 3,
wherein the first copolymer is derived from
(i) greater than 80% by weight of one or more (meth)acrylate monomers;
(ii) greater than 0% by weight to 5% by weight of one or more carboxylic acid-containing monomers;
(iii) greater than 0% by weight to 10% by weight of one or more acetoacetoxy monomers;
(iv) greater than 0% by weight to 5% by weight of one or more phosphorus-containing monomers; and
(v) optionally one or more additional ethylenically-unsaturated monomers, excluding monomers (i), (ii), (iii), and (iv).

### Claim 10 (depends on 3)

The particle of claim 3, wherein the one or more (meth)acrylate monomers are selected from the group consisting of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.

### Claim 11 (depends on 3)

The particle of claim 3, wherein
the one or more carboxylic acid-containing monomers are selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and combinations thereof;
the one or more phosphorus-containing monomers are selected from the group consisting of 2-phosphoethyl methacrylate (PEM), 2-phosphopropyl methacrylate, 3-phosphopropyl methacrylate, phosphobutyl methacrylate, 3-phospho-2-hydroxypropyl methacrylate, and combinations thereof; and
the one or more acetoacetoxy monomers are selected from the group consisting of acetoacetoxyethyl (meth)acrylate (AAEM), acetoacetoxypropyl (meth)acrylate, acetoacetoxybutyl (meth)acrylate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, allyl acetoacetate, vinyl acetoacetate, and combinations thereof.

### Claim 12 (depends on 3)

The particle of claim 3,
wherein the one or more hard ethylenically-unsaturated monomers are selected from the group consisting of methyl methacrylate, styrene, and combinations thereof.

### Claim 13 (depends on 3)

The particle of claim 3,
wherein the second polymer is derived from at least 90% by weight of one or more hard ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, styrene, and combinations thereof, based on the total weight of monomers used to form the second polymer.

### Claim 14 (depends on 3)

An aqueous composition comprising a plurality of particles defined by claim 3 dispersed in an aqueous medium.

### Claim 15 (depends on 3)

A coating comprising a plurality of particles defined by claim 3.

### Claim 16

A method of making a multilayer particle, comprising
(i) polymerizing a soft ethylenically-unsaturated monomer, a phosphorus-containing monomer, and an acetoacetoxy monomer in a first emulsion polymerization step to produce a first copolymer having a first theoretical Tg; and
(ii) polymerizing one or more hard ethylenically-unsaturated monomers in a second emulsion polymerization step to produce a second polymer having a second theoretical Tg that is at least 40° C. greater than the first theoretical Tg, wherein the one or more hard ethylenically-unsaturated monomers comprise at least 50% by weight of the monomers polymerized to form the second polymer.

### Claim 17 (depends on 16)

The method of claim 16, wherein the particle exhibits a Tg, measured using DSC, ranging from −10° C. to 25° C.

### Claim 18 (depends on 16)

The method of claim 16, wherein the first emulsion polymerization step further comprises an aryl phosphate surfactant.

### Claim 19 (depends on 18)

The method of claim 18, wherein the aryl phosphate surfactant comprises a tristyrylphenol alkoxylated phosphate surfactant.

### Claim 20 (depends on 16)

The method of claim 16, wherein the first polymerization step is carried out at a first polymerization temperature of less than or equal to 85° C., and the second polymerization step is carried out at a second polymerization temperature of less than or equal to 85° C.