EP0197635A2
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EP
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Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein
Assignee: National Starch and Chemical Investment Holding Corp
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Filing: 1986-02-18
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Granted: —
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Expires: 2006-02-18
Abstract
Abstract Acrylic emulsion copolymers are prepared by emulsion polymerization of (A) a surfactant monomer, (B) an α, β-ethylenically unsaturated carboxylic acid monomer, (C) a nonionic α, β-ethyenically unsaturated monomer and (D) optionally a polyethylenically unsaturated cross-linking monomer. The surfactant monomer is prepared by condensing an alcohol or primary amine-containing nonionic surfactant with a monoethylenically unsaturated monoisocyanate. At a low pH the copolymer may be in the form of an aqueous dispersion or latex, but thickens upon neutralization of at least some of the carboxyl groups.
Inventors
- 👤 Charles G. Ruffner
- 👤 John M. Wilkerson Iii
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-28 18:01
CPC Classifications
D; D21; D21H; D21H19/00; D21H19/36; D21H19/44; D21H19/56; D21H19/58; C; C08; C08F; C08F220/00; C08F220/02; C08F220/04; C08F246/00; C08G; C08G18/00; C08G18/06; C08G18/70; C08G18/81; C08G18/8108; C09; C09D; C09D7/00; C09D7/40; C09D7/43; C09K; C09K3/00; C09K8/00; C09K8/02; C09K8/04; C09K8/14; C09K8/18; C09K8/22; C09K8/24; C11; C11D; C11D3/00; C11D3/16; C11D3/37; C11D3/3746; C11D3/3757; C11D3/3765; D06; D06P; D06P1/00; D06P1/44; D06P1/52; D06P1/5207; D06P1/525; C08L; C08L33/00; C08L33/02; C08L33/04; C08L33/06; C08L33/08; C08L39/00
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
376 words
A copolymer obtained by aqueous emulsion copolymerization of a monomer system comprising (A) about 1 to about 25 percent of at least one nonionic urethane monomer which is the urethane reaction product of a monoethylenically unsaturated monoisocyanate with a nonionic surfactant of the formula: in which x is an integer of from 1 to 150 and y is an integer of from 0 to 50 when R is alkoxy, alkylphenoxy, dialkylphenoxy or alkyl carbonyloxy having from 5 to 30 carbon atoms, or a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and the sum of said integers is from 0 to 100 R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of 0 to 40 when R is I where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl or dialkylphenyl of from 5 to 30 carbon atoms; (B) about 5 to about 70 percent of a copolymerizable α,β -ethyenically unsaturated carboxylic acid monomer of the formula where R is H and R 1 is H, an alkyl group containing from 1 to 4 carbon atoms, or -CH 2 COOX; R is -COOH and R 1 is H, and X is H or an alkyl group containing from 1 to 4 carbon atoms, (C) about 10 to about 90 percent of at least one nonionic, copolymerizable αβ-ethylenically I unsaturated monomer of the formula where Y is H and Z is CN, Cl, -COOR 1 , -C 6 H 4 R, or -CH=CH 2 ; Y and Z are Cl, and Y is CH 3 and Z is CN, -CH=CH 2 , -C 6 H 4 R, or -COOR 1 , and R is H, Cl, Br or alkyl containing from 1 to 4 carbon atoms; R 1 is alkyl containing from 1 to 12 carbon atoms, or hydroxalkyl containing from 2 to 8 carbon atoms, and R 2 is alkyl containing from 1 to 8 carbon atoms; and (D) up to 1 percent of a copolymerizable polyethylenically unsaturated cross-linking monomer, said percentages being by weight, based on the total weight of said monomers.
Claim 2
Dependent Claim
376 words
A copolymer obtained by aqueous emulsion copolymerization of a monomer system comprising (A) about 1 to about 25 percent of at least one nonionic urethane monomer which is the urethane reaction product of a monoethylenically unsaturated monoisocyanate with a nonionic surfactant of the formula: in which x is an integer of from 1 to 150 and y is an integer of from 0 to 50 when R is alkoxy, alkylphenoxy, dialkylphenoxy or alkyl carbonyloxy having from 5 to 30 carbon atoms, or a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and the sum of said integers is from 0 to 100 R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of 0 to 40 when R is I where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl or dialkylphenyl of from 5 to 30 carbon atoms; (B) about 5 to about 70 percent of a copolymerizable α,β -ethyenically unsaturated carboxylic acid monomer of the formula where R is H and R 1 is H, an alkyl group containing from 1 to 4 carbon atoms, or -CH 2 COOX; R is -COOH and R 1 is H, and X is H or an alkyl group containing from 1 to 4 carbon atoms, (C) about 10 to about 90 percent of at least one nonionic, copolymerizable αβ-ethylenically I unsaturated monomer of the formula where Y is H and Z is CN, Cl, -COOR 1 , -C 6 H 4 R, or -CH=CH 2 ; Y and Z are Cl, and Y is CH 3 and Z is CN, -CH=CH 2 , -C 6 H 4 R, or -COOR 1 , and R is H, Cl, Br or alkyl containing from 1 to 4 carbon atoms; R 1 is alkyl containing from 1 to 12 carbon atoms, or hydroxalkyl containing from 2 to 8 carbon atoms, and R 2 is alkyl containing from 1 to 8 carbon atoms; and (D) up to 1 percent of a copolymerizable polyethylenically unsaturated cross-linking monomer, said percentages being by weight, based on the total weight of said monomers.
Claim 3
Dependent Claim
13 words
An emulsion copolymer according to claim 1 polymerized from a monomer system comprising
Claim 4
Dependent Claim
78 words
(A) about 5 to about 15 percent of said nonionic urethane monomer, (B) about 30 to about 50 percent of said αβ-ethylenically unsaturated monomer in which R is H, and R 1 is H or an alkyl group containing from 1 to 4 carbon atoms, and (C) about 30 to about 70 percent of said α,β-ethylenically unsaturated monomer in which Y is H and Z is -COOR where R is alkyl containing from 1 to 4 carbon atoms.
Claim 5
Dependent Claim
78 words
(A) about 5 to about 15 percent of said nonionic urethane monomer, (B) about 30 to about 50 percent of said αβ-ethylenically unsaturated monomer in which R is H, and R 1 is H or an alkyl group containing from 1 to 4 carbon atoms, and (C) about 30 to about 70 percent of said α,β-ethylenically unsaturated monomer in which Y is H and Z is -COOR where R is alkyl containing from 1 to 4 carbon atoms.
Claim 6
Dependent Claim
54 words
An emulsion copolymer according to claim 2 in which in said nonionic urethane monomer (A), R is a sorbitan monoester in which R 1 is an alkyl group containing from 10 to 20 carbon atoms and the sum of p, q, r and s is 10 to 20, an x and y are zero.
Claim 7
Dependent Claim
48 words
An emulsion copolymer according to claim 2 in which in said nonionic urethane monomer (A), R is -N(R 3 ) 2 where R 3 is an alkyl group containing from 5 to 15 carbon atoms, x is an integer of from 2 to 20 and y is zero.
Claim 8
Dependent Claim
180 words
A copolymer according to claim 1 or 2 in which the nonionic urethane monomer is a substituted carbonyl amino alkyl acrylate monomer of the formula: in which A is an alkylene group of the formula (CH 2 ) n where n is an integer of from 2 to 20; Z is CH 2 =CH-, or x is an integer of from 1 to 150 and y is an integer of from 0 to 50 when R is alkoxy, alkylphenoxy, dialkylphenoxy or alkyl carbonyloxy having from 5 to 30 carbon atoms, or a sorbitan fatty ester of the formula where each of p, q, r and s is an integer and the sum of said integers is from 0 to 100, R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of from 0 to 40 when R is where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl, or dialkylphenyl of from 5 to 30 carbon atoms.
Claim 9
Dependent Claim
61 words
An emulsion copolymer according to claim 5 in which said substituted carbonyl amino alkyl acrylate' monomer (A), R is alkoxy containing from 10 to 20 carbon atoms, Z is CH 2 =CH- or CH 2 =C(CH 3 )-, A is alkylene containing from 2 to 4 carbon atos, x is an integer of from 2 to 20, and y is zero.
Claim 10
Dependent Claim
64 words
An emulsion copolymer according to claim 5 in which in said substituted carbonyl amino alkyl acrylate monomer (A), R is alkylphenoxy or dialkylphenoxy containing from 8 to 20 carbon atoms, Z is CH 2 =CH- or CH 2 =C(CH 3 )-, A is alkylene containing from 2 to 4 carbon atoms, x is an integer of from 2 to 20, and y is zero.
Claim 11
Dependent Claim
78 words
An emulsion copolymer according to claim 5 in which in said substituted carbonyl amino alkyl acrylate monomer (A), R is a sorbitan monester in which R 1 is an alkyl group containing from 10 to 20 carbon atoms and the sum of p, q, r and s is 10 to 20, Z is CH 2 =CH- or CH 2 =(CH 3 ), A is alkylene containing from 2 to 4 carbon atoms, and x and y are zero.
Claim 12
Dependent Claim
30 words
An emulsion copolymer according to claim 3 or 8 in which in said monomer (A), R is sorbitan trioleate, and the sum of p, q, r and s is zero.
Claim 13
Dependent Claim
71 words
An emulsion copolymer according to claim 5 in which in said substituted carbonyl amino alkyl acryalte monomer (A), R is -N(R 3 ) 2 and R 3 is an alkyl group containing from 5 to 15 carbon atoms, Z is CH 2 =CH-or CH 2 =C(CH 3 )-, A is alkylene containing from 2 to 4 carbon atoms, x is an integer of from 2 to 20 and y is zero.
Claim 14
Dependent Claim
88 words
An emulsion copolymer according to claim 5 polymerized from a monomer system comprising (A) about 7 to about 10 percent of said substituted carbonyl amino alkyl acrylate monomer in which Z is CH 2 =C(CH 3 )-, A is ethylene, x is an integer from 2 to 20 and y is zero, (B) about 35 to about 45 percent of acrylic or methacrylic acid, (C) about 50 to about 60 percent of ethyl acrylate, and (D) about 0.5 to about 1 percent of said polyethyenically unsaturated cross-linking monomer.
Claim 15
Dependent Claim
45 words
An emulsion copolymer according to claim 11 polymerized from a monomer system comprising: (A) a substituted carbonyl amino ethyl methacrylate selected from the group consisting of poly(oxyethylene) 20 sorbitan monooleate-, and monooleyl amine-carbonyl amino ethyl methacrylate, (B) methacrylic acid, (C) ethyl acrylate, and (D) diallylphthalate.
Claim 16
Dependent Claim
66 words
An emulsion copolymer according to claim 11 polymerized from a monomer system comprising: (A) a substituted carbonyl amino ethyl methacrylate selected from the group consisting of headecyl poly(oxyethylene) 4 -, heptadecyl poly(oxyethylene) 20 -, nonylphenoxy poly (oxyethylene) 4 -, nonylphenoxy poly(oxyethylene) 20 -, dinonylphenoxy poly(oxyethylene) 9 -, poly(oxyethylene) 20 sorbitan monooleate-, and monooleyl amine-carbonyl amino ethyl methacrylate, (B) methacrylic acid, (C) ethyl acrylate, and (D) diallylphthalate.
Claim 17
Dependent Claim
36 words
An aqueous colloidal dispersion comprising from about 5 to about 50 percent, by weight, of an emulsion copolymer according to any of claims 1 to 13 having a pH of from about 2.5 to about 5.
Claim 18
Dependent Claim
46 words
A process for making the aqueous colloidal dispersion of claim 14 comprising emulsion polymerizing the monomeric system thereof at a pH of from 2.5 to about 5 in the presence of a free radical producing initiator at a temperature of from about 40° to about 90°C.
Claim 19
Dependent Claim
33 words
A process according to claim 15 in which the polymerisation temperature is from about 75° to about 85°C and a colloidal dispersion containing a copolymer according to claim 14 or 15 is produced.
Claim 20
Dependent Claim
25 words
A thickened aqueous composition containing an effective thickening amount of at least a partially neutralized emulsion copolymer according to any of claims 1 to 13.
Claim 21
Dependent Claim
43 words
A process for making a thickened aqueous composition which comprises combining with the aqueous composition an effective thickening amount of an emulsion copolymer according to any of claims 1 to 13 and at least partially neutralizing said copolymer to thus thicken said composition.
Claim 22
Dependent Claim
37 words
A thickened composition according to claim 18 comprising a latex paint, a pigment dispersion, an oil well drilling fluid, a textile printing paste, an adhesive, a liquid detergent, a paper coating composition, or a wall joint compound.
Claim 23
Dependent Claim
134 words
A nonionic urethane compound which is the urethane reaction product of a monoethylenically unsaturated monoisocyanate with a nonionic surfactant of the formula: in which x is an integer of from 1 to 150 and y is an integer of from 0 to 50 when R is a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and tne sum or said integers is from 0 to 100 R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of 0 to 40 when R is where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl or dialkylphenyl of from 5 to 30 carbon atoms.
Claim 24
Dependent Claim
134 words
A nonionic urethane compound which is the urethane reaction product of a monoethylenically unsaturated monoisocyanate with a nonionic surfactant of the formula: in which x is an integer of from 1 to 150 and y is an integer of from 0 to 50 when R is a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and tne sum or said integers is from 0 to 100 R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of 0 to 40 when R is where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl or dialkylphenyl of from 5 to 30 carbon atoms.
Claim 25
Dependent Claim
156 words
A substituted carbonyl amino alkyl acrylate compound of the formula: in which A is an alkylene group of the formula (CH 2 ) n where n is an integer of from 2 to 20; Z is CH 2 =CH-, CH 2 =C-C-0-CH 2 -CH 2 -; x is an integer of from 1 to 150 and y is aninteger of from 0 to 40 when R is a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and the sum of said integers is from 0 to 20, R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of from 0 to 40 when R is where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl, or dialkylphenyl of from 5 to 30 car.bon atoms.
Claim 26
Dependent Claim
156 words
A substituted carbonyl amino alkyl acrylate compound of the formula: in which A is an alkylene group of the formula (CH 2 ) n where n is an integer of from 2 to 20; Z is CH 2 =CH-, CH 2 =C-C-0-CH 2 -CH 2 -; x is an integer of from 1 to 150 and y is aninteger of from 0 to 40 when R is a sorbitan fatty ester of the formula: where each of p, q, r and s is an integer and the sum of said integers is from 0 to 20, R 1 is H or -COR 2 and R 2 is alkyl, alkylphenyl, or dialkylphenyl having 5 to 30 carbon atoms; or x and y are each integers of from 0 to 40 when R is where R 2 is H or R 3 , and R 3 is alkyl, alkylphenyl, or dialkylphenyl of from 5 to 30 car.bon atoms.
Claim 27
Dependent Claim
36 words
A compound according to claim 21 or 22 in which R, x and y and (when present) A and Z are as defined in claim 8, 9 or 10.or which is as defined in claim 12.
Claim 28
Dependent Claim
16 words
I have noticed two typographical errors in claim 1 on page 42 of the text filed.
Claim 29
Dependent Claim
22 words
At line 6 the words "R is -COOH" should be "R is -COOX", and at line 15 should be inserted after "CN,".
Claim 30
Dependent Claim
22 words
At line 6 the words "R is -COOH" should be "R is -COOX", and at line 15 should be inserted after "CN,".
Claim 31
Dependent Claim
34 words
The above corrections will bring claim 1 into agreement with the statement of invention at lines 12 and 23 of page 7 and I request that the corrections be allowed under Rule 88 EPC.
References Cited (Backward Citations)
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