Aqueous dispersion of copolymer particles of vinyl acetate and a cyclic ketene acetal monomer

Patent metadata

Field	Value
Publication number	US-11111328-B2
Application number	US-202016822256-A
Country	US
Kind code	B2
Filing date	Mar 18, 2020
Priority date	Apr 10, 2019
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

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.

First claim

The invention claimed is:

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 C 1 -C 6 -alkyl;
R 1 and R 2 are each independently H, C 1 -C 12 -alkyl, phenyl, or vinyl; or R 1 and R 2 together with the carbon atoms to which they are attached, form a fused benzene ring or a fused C 3 -C 7 -cycloaliphatic ring; and
R 1′ and R 2′ are each independently H or C 1 -C 12 -alkyl; or R 1 and R 1′ and/or R 2 and R 2′ form an exocyclic double bond;
with the proviso that when n is 1:
R 3 and R 3′ are each independently H, C 1 -C 12 -alkyl, phenyl, or R 3 and R 3′ 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 R 3 is H, C 1 -C 12 -alkyl, or together with the carbon atoms to which they are attached form a double bond, a fused benzene ring, or a fused C 3 -C 7 -cycloaliphatic ring.

2. 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.

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

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.

9. 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.

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 C 1 -C 6 -alkyl;
R 1 and R 2 are each independently H, C 1 -C 12 -alkyl, phenyl, or vinyl; or R 1 and R 2 together with the carbon atoms to which they are attached, form a fused benzene ring or a fused C 3 -C 7 -cycloaliphatic ring; and
R 1′ and R 2′ are each independently H or C 1 -C 12 -alkyl; or R 1 and R 1′ and/or R 2 and R 2′ form an exocyclic double bond;
with the proviso that when n is 1:
R 3 and R 3′ are each independently H, C 1 -C 12 -alkyl, phenyl, or R 3 and R 3′ 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 R 3 is H, C 1 -C 12 -alkyl, or together with the carbon atoms to which they are attached form a double bond, a fused benzene ring, or a fused C 3 -C 7 -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.

11. 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.

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

13. 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.

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.

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

Assignees

• Rohm & Haas

Inventors

• Carter Matthew
• Defelippis James
• Even Ralph C
• Hejl Andrew

Classifications

• C08L31/04 Primary

  Homopolymers or copolymers of vinyl acetate · CPC title

• C08L2201/52

  Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C · CPC title

• C08J3/03

  in aqueous media · CPC title

• C08G2/26 Primary

  with compounds containing carbon-to-carbon unsaturation · CPC title

• C08F218/08 Primary

  Vinyl acetate · CPC title