US4384096A
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Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
Assignee: Dow Chemical Co
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Filing: 1980-12-23
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Granted: 1983-05-17
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Expires: 2000-12-23
Abstract
Abstract Novel aqueous liquid emulsion polymers are prepared by the copolymerization of (A) about 15-60 weight percent of a C 3 -C 8 α,β-ethylenically unsaturated carboxylic acid monomer, preferably acrylic or methacrylic acid or a mixture thereof with itaconic or fumaric acid, (B) about 15-80 weight percent of a nonionic copolymerizable C 2 -C 12 α,β-ethylenically unsaturated monomer, preferably a monovinyl ester such as ethyl acrylate or a mixture thereof with styrene, acrylonitrile, vinyl chloride or vinyl acetate, and (C) about 1-30 weight percent of certain nonionic vinyl surfactant esters, such as nonylphenoxypoly(ethyleneoxy) 9 ethyl acrylate, to give an emulsion copolymer stable as an aqueous colloidal dispersion at an acid pH lower than about 5.0 but responsive to pH adjustment with base. These emulsion polymers adjusted to a pH of about 5.5 or higher are effective thickeners for a wide variety of aqueous systems including cosmetic products, drilling muds, and particularly aqueous coating compositions such as latex paint.
Inventors
- 👤 Lawrence F. Sonnabend
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 22:19
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/52; C07C69/533; C07C69/54; C08; C08F; C08F246/00; C08F290/00; C08F290/02; C08F290/06; C08F290/062; C09; C09D; C09D7/00; C09D7/40; C09D7/43; C08F220/00; C08F220/02; C08F220/10; C08F220/26; C08F220/28; C08F220/285; C08F220/286; C08L; C08L33/00; C08L33/02; C08L33/04; C08L33/06; C08L33/08
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
303 words
A liquid emulsion polymer useful as a pH responsive thickener for aqueous compositions comprising an aqueous emulsion copolymer of: A. about 15-60 weight percent based on total monomers of at least one C 3 -C 8 α,β-ethylenically unsaturated carboxylic acid monomer of the formula: ##STR10## where R is H and R' is H, C 1 -C 4 alkyl, or --CH 2 COOX; R is --COOX and R' is H or --CH 2 COOX; or, R is CH 3 and R' is H; and X is H or C 1 -C 4 alkyl; B. about 15-80 weight percent of at least one nonionic, copolymerizable C 2 -C 12 α,β-ethylenically unsaturated monomer of the formula: CH.sub.2 ═CYZ (II) where Y is H and Z is --COOR, --C 6 H 4 R', CN, Cl, ##STR11## or --CH═CH 2 ; Y is CH 3 and Z is --COOR, --C 6 H 4 R', CN or --CH═CH 2 ; or Y and Z are Cl; and R is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl; R' is H, Cl, Br, or C 1 -C 4 alkyl; and R" is C 1 -C 8 alkyl; and C. about 1-30 weight percent based on total monomers of at least one nonionic vinyl surfactant ester of the formula: ##STR12## where R is H or CH 3 , each R' is C 1 -C 2 alkyl, R" is C 8 -C 20 alkyl or C 8 -C 16 alkylphenyl, n is an average number from about 6-100 and m is an average number from about 0-50 provided that n≧m and Σ(n+m) is about 6-100; said polymer being stable as an aqueous colloidal dispersion at a pH lower than about 5.0 but becoming an effective thickener for aqueous systems upon adjustment to a pH of about 5.5-10.5 or higher.
Claim 2
Dependent Claim
303 words
A liquid emulsion polymer useful as a pH responsive thickener for aqueous compositions comprising an aqueous emulsion copolymer of: A. about 15-60 weight percent based on total monomers of at least one C 3 -C 8 α,β-ethylenically unsaturated carboxylic acid monomer of the formula: ##STR10## where R is H and R' is H, C 1 -C 4 alkyl, or --CH 2 COOX; R is --COOX and R' is H or --CH 2 COOX; or, R is CH 3 and R' is H; and X is H or C 1 -C 4 alkyl; B. about 15-80 weight percent of at least one nonionic, copolymerizable C 2 -C 12 α,β-ethylenically unsaturated monomer of the formula: CH.sub.2 ═CYZ (II) where Y is H and Z is --COOR, --C 6 H 4 R', CN, Cl, ##STR11## or --CH═CH 2 ; Y is CH 3 and Z is --COOR, --C 6 H 4 R', CN or --CH═CH 2 ; or Y and Z are Cl; and R is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl; R' is H, Cl, Br, or C 1 -C 4 alkyl; and R" is C 1 -C 8 alkyl; and C. about 1-30 weight percent based on total monomers of at least one nonionic vinyl surfactant ester of the formula: ##STR12## where R is H or CH 3 , each R' is C 1 -C 2 alkyl, R" is C 8 -C 20 alkyl or C 8 -C 16 alkylphenyl, n is an average number from about 6-100 and m is an average number from about 0-50 provided that n≧m and Σ(n+m) is about 6-100; said polymer being stable as an aqueous colloidal dispersion at a pH lower than about 5.0 but becoming an effective thickener for aqueous systems upon adjustment to a pH of about 5.5-10.5 or higher.
Claim 3
Dependent Claim
25 words
The polymer of claim 1 where the carboxylic acid monomer (A) is methacrylic acid, acrylic acid, or a mixture thereof with fumaric or itaconic acid.
Claim 4
Dependent Claim
24 words
The polymer of claim 1 containing about 33-55 weight percent of methacrylic acid or a mixture thereof with a minor amount of itaconic acid.
Claim 5
Dependent Claim
27 words
The polymer of claim 1 where the comonomer (B) is a monovinyl ester or a mixture thereof with styrene, 2-hydroxyethyl acrylate, acrylonitrile, vinyl chloride or vinyl acetate.
Claim 6
Dependent Claim
12 words
The polymer of claim 1 where the comonomer (B) is ethyl acrylate.
Claim 7
Dependent Claim
25 words
The polymer of claim 1 where the amount of the carboxylic acid monomer (A) is from about 25 weight percent to about 60 weight percent.
Claim 8
Dependent Claim
112 words
The polymer of claim 6 where the vinyl surfactant ester is selected from the group consisting of: (1) alkylphenoxypoly(ethyleneoxy)ethyl acrylates of the formula: ##STR13## where R is H or CH 3 ; Y' is C 8 -C 16 alkyl, and n is about 6-100; (2) alkoxypoly(ethyleneoxy)ethyl acrylates of the formula: ##STR14## where R is H or CH 3 , R" is C 8 -C 20 alkyl, and n is about 6-50; and (3) alkoxypoly(alkyleneoxy)ethyl acrylates of the formula: ##STR15## where R is H or CH 3 , each R' is C 1 -C 2 alkyl, R" is C 8 -C 20 alkyl, and, n is about 6-50 and m is about 1-40.
Claim 9
Dependent Claim
61 words
The polymer of claim 1 consisting essentially of: A. about 35-55 weight percent of methacrylic acid, acrylic acid or mixtures thereof with fumaric or itaconic acid; B. about 35-50 weight percent of ethyl acrylate or mixtures thereof with styrene, 2-hydroxyethyl acrylate, acrylonitrile, vinyl chloride or vinyl acetate; and C. about 2-20 weight percent of a vinyl surfactant ester of Formula III.
Claim 10
Dependent Claim
38 words
The polymer of claim 8 wherein the vinyl surfactant ester is an alkylphenoxypoly(ethyleneoxy)ethyl acrylate of the formula: ##STR16## where R is H or CH 3 ; Y' is C 8 -C 16 alkyl, and n is about 6-100.
Claim 11
Dependent Claim
38 words
The polymer of claim 8 wherein the vinyl surfactant ester is an alkoxypoly(ethyleneoxy)ethyl acrylate of the formula: ##STR17## where R is H or CH 3 , R" is C 8 -C 20 alkyl, and n is about 6-50.
Claim 12
Dependent Claim
51 words
The polymer of claim 8 wherein the vinyl surfactant ester is an alkoxypoly(alkyleneoxy)ethyl acrylate of the formula: ##STR18## where R is H or CH 3 , each R' is C 1 -C 2 alkyl, R" is C 8 -C 20 alkyl, and, n is about 6-50 and m is about 1-40.
Claim 13
Dependent Claim
44 words
The polymer of claim 1 consisting essentially of: A. about 40-50 weight percent of methacrylic acid; B. about 35-50 weight percent of ethyl acrylate; and C. about 2-12 weight percent of the methacrylic ester of a nonylphenoxypoly(ethyleneoxy) n ethanol where n is about 6-40.
Claim 14
Dependent Claim
29 words
The polymer of claim 12 wherein about 1-15 weight percent of itaconic acid based on the total monomeric weight is substituted for a minor portion of the methacrylic acid.
Claim 15
Dependent Claim
20 words
The polymer of claim 13 containing about 40-45 weight percent of methacrylic acid and 2-10 weight percent of itaconic acid.
Claim 16
Dependent Claim
38 words
The polymer of claim 1 having an average particle size of about 500-3000 A and a Brookfield viscosity of about 50-50,000 cps as a 1 percent aqueous solution in ammonium salt form at pH 9.0 and 25° C.
Claim 17
Dependent Claim
34 words
A liquid aqueous colloidal dispersion useful as a pH responsive polymeric thickener for aqueous compositions and containing about 10-50 weight percent of the polymer of claim 1 and having a pH of about 2.5-5.0.
Claim 18
Dependent Claim
50 words
The liquid aqueous colloidal dispersion of claim 16 where the polymer consists essentially of: A. about 40-50 weight percent of methacrylic acid; B. about 35-50 weight percent of ethyl acrylate; and C. about 2-12 weight percent of the methacrylic ester of a nonylphenoxypoly(ethyleneoxy) n ethanol where n is about 6-40.
Claim 19
Dependent Claim
39 words
A process for making the liquid aqueous colloidal dispersion of claim 16 comprising emulsion copolymerizing the monomeric mixture at a pH of about 2.5-5.0 in the presence of a free-radical producing initiator at a temperature between about 60°-90° C.
Claim 20
Dependent Claim
45 words
The process of claim 18 wherein the emulsion copolymerization gives a polymer having an average particle size of about 500-3000 A and a Brookfield viscosity of about 50-50,000 cps as a 1 percent aqueous solution in ammonium salt form at pH 9.0 and 25° C.
Claim 21
Dependent Claim
80 words
The process of claim 18 wherein the monomeric mixture consists essentially of: A. about 40-50 weight percent of methacrylic acid; B. about 35-50 weight percent of ethyl acrylate or a mixture thereof with styrene, 2-hydroxyethyl acrylate, acrylonitrile, vinyl chloride, or vinyl acetate; and C. about 2-12 weight percent of the methacrylic ester of an alkylphenoxypoly(ethyleneoxy)ethyl acrylate of the formula: ##STR19## where R is H or CH 3 ; Y' is C 8 -C 16 alkyl, and n is about 6-100.
Claim 22
Dependent Claim
35 words
A thickened aqueous composition having a pH within the range of about 6.5-11.0 comprising an aqueous composition containing a water-soluble or dispersible material and an effective amount of a liquid emulsion polymer of claim 1.
Claim 23
Dependent Claim
17 words
The thickened aqueous composition of claim 21 wherein the aqueous composition is a slurry of titanium dioxide.
Claim 24
Dependent Claim
19 words
The thickened aqueous composition of claim 21 wherein the aqueous composition is a colloidal dispersion of a water-insoluble polymer.
Claim 25
Dependent Claim
18 words
The thickened aqueous composition of claim 21 wherein the aqueous composition is a natural, synthetic or artificial latex.
Claim 26
Dependent Claim
51 words
The thickened aqueous composition of claim 21 wherein the liquid emulsion polymer consists essentially of: A. about 40-50 weight percent of methacrylic acid; B. about 35-50 weight percent of ethyl acrylate; and C. about 2-12 weight percent of the methacrylic ester of a nonylphenoxypoly(ethyleneoxy) n ethanol where n is about 6-40.
Claim 27
Dependent Claim
61 words
A process for making a thickened aqueous composition which comprises: (1) blending with the aqueous composition a sufficient amount of the liquid emulsion polymer of claim 1 to thicken the aqueous coating composition and (2) adjusting the pH of said blend within a range of about 6.5-11.0 as necessary to dissolve the emulsion polymer therein and thus thicken the aqueous composition.
Claim 28
Dependent Claim
17 words
The process of claim 26 wherein the aqueous composition is a colloidal dispersion of a water-insoluble polymer.
Claim 29
Dependent Claim
16 words
The process of claim 26 wherein the aqueous composition is a natural, synthetic or artificial latex.
Claim 30
Dependent Claim
13 words
The process of claim 26 wherein the aqueous composition is a synthetic latex.
Claim 31
Dependent Claim
67 words
The process of claim 26 wherein the liquid emulsion polymer consists essentially of: A. about 40-50 weight percent of methacrylic acid; B. about 35-50 weight percent of ethyl acrylate; and C. about 2-12 weight percent of the methacrylic ester of an alkylphenoxypoly(ethyleneoxy)ethyl acrylate of the formula: ##STR20## where R is H or CH 3 ; Y' is C 8 -C 16 alkyl; and n is about 6-100.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-05-16 | 1986-11-15 | 1987-05-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-05-16 | 1990-11-15 | 1991-05-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-05-16 | 1994-11-15 | 1995-05-17 | $7700.00 | Window Closed / Lapsed |