# US 11,111,328 B2 · Aqueous dispersion of copolymer particles of vinyl acetate and a cyclic ketene acetal monomer

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- Number: US 11,111,328 B2
- Document ID: US11111328B2
- Status: Granted
- Kind: B2
- Application number: 16/822,256
- Filed: 2020-03-18
- Published: 2020-10-15
- Granted: 2021-09-07
- Earliest claimed: 2019-04-10
- Assignees: Rohm and Haas Company
- Applicants: Rohm and Haas Company
- Inventors: Matthew Carter; James DeFelippis; Ralph C. Even; Andrew Hejl
- Web page: https://patentgrep.com/patent/US11111328B2

## CPC

- C08F 218/08: Vinyl acetate
- C09D 131/04: Homopolymers or copolymers of vinyl acetate
- C08G 63/005: {Polyesters prepared from ketenes}
- C08L 31/04: Homopolymers or copolymers of vinyl acetate
- C08F 2800/20: as weight or mass percentages
- C08L 2201/52: Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- 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)

## Abstract

The present invention relates to a composition comprising an aqueous dispersion of copolymer particles comprising structural units of vinyl acetate, a cyclic ketene acetal monomer, and a monoethylenically unsaturated acid monomer, or a salt thereof; wherein the cyclic ketene acetal monomer is characterized by following structure: where n and the R groups are as defined herein. The composition of the present invention provides a water-borne dispersion that is substantially free of volatile organic solvents and that provides a readily degradable polymer that is useful, for example, in the manufacture of biodegradable packaging products.

## Claims

### Claim 1

A composition comprising an aqueous dispersion of copolymer particles having a z-average particle size in the range of from 50 nm to 500 nm, which polymer particles comprise, based on the weight of the copolymer particles, a) from 75 to 98.5 weight percent structural units of vinyl acetate; b) from 1 to 20 weight percent structural units of a cyclic ketene acetal monomer; and c) from 0.05 to 5 weight percent structural units of a monoethylenically unsaturated acid monomer, or a salt thereof; wherein the cyclic ketene acetal monomer is characterized by following structure:
where n is 0, 1, or 2;
R is H or C1-C6-alkyl;
R1 and R2 are each independently H, C1-C12-alkyl, phenyl, or vinyl; or R1 and R2 together with the carbon atoms to which they are attached, form a fused benzene ring or a fused C3-C7-cycloaliphatic ring; and
R1′ and R2′ are each independently H or C1-C12-alkyl; or R1 and R1′ and/or R2 and R2′ form an exocyclic double bond;
with the proviso that when n is 1:
R3 and R3′ are each independently H, C1-C12-alkyl, phenyl, or R3 and R3′ form an exocyclic double bond or a spirocycloaliphatic group or spiro-2-methylene-1,3-dioxepane group;
with the further proviso that when n is 2:
each R3 is H, C1-C12-alkyl, or together with the carbon atoms to which they are attached form a double bond, a fused benzene ring, or a fused C3-C7-cycloaliphatic ring.

### Claim 2 (depends on 1)

The composition of claim 1 wherein the polymer particles comprise, based on the weight of the polymer particles, a) from 85 to 96.5 weight percent structural units of vinyl acetate; b) from 3 to 15 weight percent structural units of the cyclic ketene acetal monomer; and c) from 0.1 to 1 weight percent structural units of the monoethylenically unsaturated acid monomer.

### Claim 3 (depends on 2)

The composition of claim 2 wherein cyclic ketene acetal monomer is selected from the group consisting of:

### Claim 4 (depends on 3)

The composition of claim 3 wherein the cyclic ketene acetal monomer is 2-methylene-1,3-dioxepane and the acid monomer is a sulfur acid containing monomer or a salt thereof; wherein the composition further comprises less than 20 weight percent 4-hydroxybutyl acetate based on the weight of structural units of 2-methylene-1,3-dioxepane in the polymer particles.

### Claim 5 (depends on 4)

The composition of claim 4 wherein the sulfur acid containing monomer or salt thereof is selected from the group consisting of 2-acrylamido-2-methyl-1-propanesulfonic acid, salts of 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl sulfonic acid, salts of vinyl sulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, 2-propene-1-sulfonic acid and salts of 2-propene-1-sulfonic acid.

### Claim 6 (depends on 5)

The composition of claim 5 wherein the sulfur acid containing monomer or salt thereof is a salt of 2-acrylamido-2-methyl-1-propanesulfonic acid.

### Claim 7 (depends on 1)

The composition of claim 1 wherein the z-average particle size of the copolymer particles is in the range of from 80 nm to 300 nm.

### Claim 8 (depends on 5)

The composition of claim 5 which further comprises less than 10 weight percent 4-hydroxybutyl acetate based on the weight of structural units of 2-methylene-1,3-dioxepane in the polymer particles.

### Claim 9 (depends on 8)

The composition of claim 8 which further comprises less than 2 weight percent 4-hydroxybutyl acetate based on the weight of structural units of the cyclic ketene acetal monomer.

### Claim 10

A composition comprising an aqueous dispersion of copolymer particles having a z-average particle size in the range of from 50 nm to 500 nm, which polymer particles comprise, based on the weight of the copolymer particles, a) from 85 to 96.5 weight percent structural units of vinyl acetate; b) from 3 to 15 weight percent structural units of a cyclic ketene acetal monomer; and c) from 0.05 to 5 weight percent structural units of a sulfur acid containing monomer, or a salt thereof; wherein the cyclic ketene acetal monomer is characterized by following structure:
where n is 0, 1, or 2;
R is H or C1-C6-alkyl;
R1 and R2 are each independently H, C1-C12-alkyl, phenyl, or vinyl; or R1 and R2 together with the carbon atoms to which they are attached, form a fused benzene ring or a fused C3-C7-cycloaliphatic ring; and
R1′ and R2′ are each independently H or C1-C12-alkyl; or R1 and R1′ and/or R2 and R2′ form an exocyclic double bond;
with the proviso that when n is 1:
R3 and R3′ are each independently H, C1-C12-alkyl, phenyl, or R3 and R3′ form an exocyclic double bond or a spirocycloaliphatic group or spiro-2-methylene-1,3-dioxepane group;
with the further proviso that when n is 2:
each R3 is H, C1-C12-alkyl, or together with the carbon atoms to which they are attached form a double bond, a fused benzene ring, or a fused C3-C7-cycloaliphatic ring;
wherein the sulfur acid containing monomer is selected from the group consisting of 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl sulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, and 2-propene-1-sulfonic acid.

### Claim 11 (depends on 10)

The composition of claim 10 which further comprises less than 20 weight percent of hydrolysis byproducts of the vinyl acetate and the cyclic ketene acetal.

### Claim 12 (depends on 10)

The composition of claim 10 wherein cyclic ketene acetal monomer is selected from the group consisting of:

### Claim 13 (depends on 12)

The composition of claim 12 wherein the cyclic ketene acetal monomer is 2-methylene-1,3-dioxepane and the acid monomer is 2-acrylamido-2-methyl-1-propanesulfonic acid or a salt thereof; and wherein the composition further comprises less than 10 weight percent 4-hydroxybutyl acetate based on the weight of structural units of 2-methylene-1,3-dioxepane in the polymer particles.

### Claim 14

A composition comprising an aqueous dispersion of copolymer particles having a z-average particle size in the range of from 50 nm to 500 nm, which polymer particles comprise, based on the weight of the copolymer particles, a) from 85 to 96.5 weight percent structural units of vinyl acetate; b) from 3 to 15 weight percent structural units of 2-methylene-1,3-dioxepane; c) from 0.05 to 5 weight percent structural units of a monoethylenically unsaturated acid monomer; and d) less than 5 weight percent 4-hydroxybutyl acetate based on the weight of structural units of 2-methylene-1,3-dioxepane in the polymer particles.

### Claim 15 (depends on 14)

The composition of claim 14 wherein the monoethylenically unsaturated acid monomer is 2-acrylamido-2-methyl-1-propanesulfonic acid or a salt thereof.