# US 11,440,978 B2 · Polymer dispersions, their preparation and use

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- Number: US 11,440,978 B2
- Document ID: US11440978B2
- Status: Granted
- Kind: B2
- Application number: 17/250,136
- Filed: 2019-05-30
- Published: 2021-07-29
- Granted: 2022-09-13
- Earliest claimed: 2018-06-07
- Assignees: Celanese International Corporation
- Applicants: Celanese International Corporation
- Inventors: Kerstin Wenzel; Matthias Junk; Thomas Fichtner; Stephan Krieger
- Web page: https://patentgrep.com/patent/US11440978B2

## CPC

- C08F 2/22: Emulsion polymerisation
- 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 218/08: Vinyl acetate
- C08F 218/10: of monocarboxylic acids containing three or more carbon atoms
- C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 230/085: {the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes}
- C08F 263/04: on to polymers of vinyl acetate
- C08K 3/013: Fillers, pigments or reinforcing additives
- C09D 5/02: Emulsion paints {including aerosols}
- 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 2800/20: as weight or mass percentages
- 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)
- 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

A multistage emulsion polymerization process comprises polymerizing a first monomer composition comprising from 50 to 95 weight percent of vinyl acetate, from 5 to 40 weight percent of at least one vinyl ester of a C5 to C18 unsaturated carboxylic acid, and optionally up to 40 weight percent of ethylene, all based on the total weight of monomers in the first monomer composition, to produce a first stage polymer. A second monomer composition comprising 40 to 89.95 weight percent of at least one ester of methacrylic acid or a vinyl aromatic monomer, 10 to 59.95 weight percent of at least one ester of acrylic acid, and from 0.05 to 10 weight percent of at least one comonomer with acid functionality, based on the total weight of monomers in the second monomer composition, is then polymerized in the presence of the first stage polymer to produce a second stage polymer.

## Claims

### Claim 1

An emulsion polymerization process comprising:
(i) polymerizing, in a first stage, a first monomer composition comprising from 50 weight percent to 95 weight percent of vinyl acetate, from 5 weight percent to 40 weight percent of at least one vinyl ester of a C5 to C18 unsaturated carboxylic acid, optionally up to 40 weight percent of ethylene, optionally up to 40 weight percent of at least one alkyl ester of acrylic acid, and optionally up to 20 weight percent of one or more further monomers copolymerizable therewith, all based on the total weight of monomers in the first monomer composition, to produce a first stage polymer; and
(ii) polymerizing, in a second stage and in the presence of said first stage polymer, a second monomer composition comprising 40 weight percent to 89.95 weight percent of at least one alkyl ester of methacrylic acid or a vinyl aromatic monomer, 10 weight percent to 59.95 weight percent of at least one alkyl ester of acrylic acid, and from 0.05 weight percent to 10 weight percent of at least one comonomer with acid functionality, based on the total weight of monomers in the second monomer composition, to produce a second stage polymer,
wherein the weight ratio of the first stage polymer to the second stage polymer is from 95:5 to 25:75.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the first stage polymer has a lower glass transition temperature, Tg, than the second stage polymer.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the glass transition temperature Tg of the first stage polymer is at least 5° C., preferably at least 10° C., lower than the second stage polymer.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the first stage polymer has a Tg less than 30° C., preferably from −15 to 25° C., more preferably from −5 to 15° C.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the second stage polymer has a Tg of 5 to 90° C., such as from 15 to 80° C., preferably from 25 to 70° C.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the at least one vinyl ester of a C5 to C18 unsaturated carboxylic acid comprises a vinyl ester of a C7 to C15 branched chain unsaturated carboxylic acid.

### Claim 7 (depends on 6)

The process according to claim 6, wherein the at least one vinyl ester of a C7 to C15 branched chain unsaturated carboxylic acid comprises a vinyl ester of a C9 to C11 branched chain unsaturated carboxylic acid.

### Claim 8 (depends on 1)

The process according to claim 1, wherein the first monomer composition comprises from 5 weight percent to 40 weight percent ethylene, based on the based on the total weight of monomers in the first monomer composition.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the at least one ester of acrylic acid in the first monomer composition comprises ethyl acrylate, n-butyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and mixtures thereof.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the first monomer composition further comprises from 0.05 weight percent to about 5 weight percent of at least one monomer selected from the group consisting of ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic and phosphoric acids, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic amides, ethylenically unsaturated carboxylic anhydrides and mixtures thereof, based on the total weight of monomers in the first monomer composition.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the first monomer composition further comprises from 0.05 weight percent to about 3 weight percent of at least one unsaturated silane monomer, based on the total weight of monomers in the first monomer composition.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the second monomer composition comprises at least 60 weight percent, preferably at least 80 weight percent, more preferably at least 90 weight percent, based on the total weight of monomers in the second monomer composition, of the at least one ester of acrylic acid and the at least one ester of methacrylic acid.

### Claim 13 (depends on 1)

The process according to claim 1, wherein the second monomer composition contains less than 5 weight percent of any vinylaromatic monomer, based on the total weight of monomers in the second monomer composition, and preferably is free of any vinyl aromatic monomer.

### Claim 14 (depends on 1)

The process according to claim 1, wherein the at least one ester of methacrylic acid in the second monomer composition comprises methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate or mixtures thereof.

### Claim 15 (depends on 1)

The process according to claim 1, wherein the at least one ester of acrylic acid in the second monomer composition comprises ethyl acrylate, n-butyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and mixtures thereof.

### Claim 16 (depends on 1)

The process according to claim 1, wherein the second monomer composition comprises from 0.1 weight percent to 10 weight percent, preferably from 0.5 weight percent to 8 weight percent, more preferably from 1 weight percent to 6 weight percent, based on the total weight of monomers in the second monomer composition, of the at least one comonomer with acid functionality.

### Claim 17 (depends on 1)

The process according to claim 1, wherein the at least one comonomer with acid functionality of the second monomer composition comprises at least one monomer selected from the group consisting of ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic and phosphoric acids, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic anhydrides and mixtures thereof.

### Claim 18 (depends on 1)

The process according to claim 1, wherein the at least one comonomer with acid functionality of the second monomer composition comprises at least one monomer selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic anhydrides and mixtures thereof.

### Claim 19 (depends on 1)

The process according to claim 1, wherein the at least one comonomer with acid functionality of the second monomer composition comprises methacrylic acid, acrylic acid, or mixtures thereof.

### Claim 20 (depends on 1)

An emulsion polymerization process according to claim 1, wherein the second monomer composition further comprises from about 0.05 weight percent to about 5 weight percent, based on the total weight of monomers in the second monomer composition, of an ethylenically unsaturated carboxylic amide.

### Claim 21 (depends on 1)

A polymer dispersion produced by the process of claim 1.

### Claim 22 (depends on 21)

The polymer dispersion of claim 21 and having a minimum film forming temperature of less than 20° C., preferably less than 10° C., more preferably equal or less than 6° C.

### Claim 23 (depends on 21)

The polymer dispersion of claim 21, wherein the particles of the polymer dispersion have a weight-averaged diameter of less than 200 nm, preferably less than 150 nm, as measured by laser diffraction and polarization intensity differential scattering (PIDS) using a Beckman Coulter LS 13320 Particle Size Analyzer.

### Claim 24 (depends on 21)

A coating composition comprising the polymer dispersion of claim 21, at least one pigment and/or at least one filler.

### Claim 25 (depends on 23)

The coating composition of claim 23, wherein the coating is a wood protection paint.

### Claim 26 (depends on 23)

The coating composition of claim 23, wherein the coating is a façade paint.

### Claim 27 (depends on 23)

The coating composition of claim 23, wherein the coating is a plaster.

### Claim 28 (depends on 23)

A coating produced from the coating composition of claim 23 and having a liquid water transmission rate w24 of less than 0.1 kg m−2h−0.5 as measured according to DIN EN 1062-3.

### Claim 29 (depends on 23)

A coating produced from paint composition of claim 23 and having a liquid water transmission rate w24 of less than 0.2 kg m−2h−0.5 during the initial immersion in water, as measured according to DIN EN 1062-3.

### Claim 30 (depends on 27)

A thermal insulation system comprising the plaster composition of claim 27.