Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein

Claim 2

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: ##STR15## in which x is an integer of from 1 to 150 and y is an integer of from 0 to 40 when R a sorbitan fatty ester of the formula ##STR16## 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 5 to 30 carbon atoms; or x and y are each integers of from 0 to 40 when R is --NH(CH 2 ) 3 O--R 3 , or ##STR17## 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-ethylenically unsaturated carboxylic acid monomer of the formula ##STR18## 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 --COOX and R 1 is H, and X is H or an alkyl group containing from 1 to 4 carbon atoms, (C) about 10 to to about 90 percent of at least one nonionic, copolymerizable α,β-ethylenically unsaturated monomer of the formula CH.sub.2 ═CYZ where Y is H and Z is CN, Cl, --COOR, C 6 H 4 R, ##STR19## or --CH═CH 2 ; Y and Z are Cl, and Y is CH 3 and Z is CN, ##STR20## --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 hydroxyalkyl 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

An emulsion copolymer according to claim 1 polymerized from a monomer system comprising (A) about 5 to about 15 percent of said nonionic urethane monomer, (B) about 30 to about 50 percent of said α,β-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 4

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, and x and y are zero.

Claim 5

An emulsion coploymer according to claim 3 in which in said nonionic urethane monomer (A), R is sorbitan trioleate, and the sum of p, q, r and s is zero.

Claim 6

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 7

A copolymer obtained by aqueous emulsion copolymerization of a monomer system comprising (A) about 1 to about 25 percent of at least one substituted carbonyl amino alkyl acrylate monomer of the formula: ##STR21## 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(CH 3 )--, CH 2 ═C(Cl)--, CH 3 CH═CH--, or ##STR22## x is an integer of from 1 to 150 and y is an integer of from 0 to 40 when R a sorbitan fatty ester of the formula ##STR23## 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 --NH(CH 2 ) 3 O--R 3 , or ##STR24## 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-ethylenically unsaturated carboxylic acid monomer of the formula ##STR25## 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 --COOX and R 1 is H, and X is H or an alkyy group containing from 1 to 4 carbon atoms, (C) about 10 to to about 90 percent of at least one nonionic, copolymerizable α,β-ethylenically unsaturated monomer of the formula CH.sub.2 ═CYZ where Y is H and Z is CN, Cl, --COOR, --C 6 H 4 R, ##STR26## or --CH═CH 2 ; Y and Z are Cl, and Y is CH 3 and Z is CN, ##STR27## --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 hydroxyalkyl 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 8

A copolymer obtained by aqueous emulsion copolymerization of a monomer system comprising (A) about 1 to about 25 percent of at least one substituted carbonyl amino alkyl acrylate monomer of the formula: ##STR21## 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(CH 3 )--, CH 2 ═C(Cl)--, CH 3 CH═CH--, or ##STR22## x is an integer of from 1 to 150 and y is an integer of from 0 to 40 when R a sorbitan fatty ester of the formula ##STR23## 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 --NH(CH 2 ) 3 O--R 3 , or ##STR24## 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-ethylenically unsaturated carboxylic acid monomer of the formula ##STR25## 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 --COOX and R 1 is H, and X is H or an alkyy group containing from 1 to 4 carbon atoms, (C) about 10 to to about 90 percent of at least one nonionic, copolymerizable α,β-ethylenically unsaturated monomer of the formula CH.sub.2 ═CYZ where Y is H and Z is CN, Cl, --COOR, --C 6 H 4 R, ##STR26## or --CH═CH 2 ; Y and Z are Cl, and Y is CH 3 and Z is CN, ##STR27## --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 hydroxyalkyl 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 9

An emulsion copolymer according to claim 6 polymerized from a monomer system comprising (A) about 5 to about 15 percent of said substituted carbonyl amino alkyl acrylate monomer, (B) about 30 to about 50 percent of said α,β-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 10

An emulsion copolymer according to claim 7 in which in said substituted carbonyl amino alkyl acrylate 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, 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 11

An emulsion coploymer according to claim 8 in which in said substituted carbonyl amine alkyl acrylate monomer (A), R is sorbitan trioleate, and the sum of p, q, r and s is zero.

Claim 12

An emulsion copolymer according to claim 7 in which in said substituted carbonyl amino alkyl acrylate monomer (A), R is --N(R 3 ) 2 where 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 13

An emulsion copolymer according to claim 6 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 polyethylenically unsaturated cross-linking monomer.

Claim 14

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 15

An aqueous colloidal dispersion comprising from about 5 to about 50 percent, by weight, of an emulsion copolymer of claim 6 having a pH of from about 2.5 to about 5.

Claim 16

An aqueous colloidal dispersion comprising from about 5 to about 50 percent, by weight, of an emulsion copolymer of claim 12 having a pH of from about 2.5 to about 5.

Claim 17

A process for making the aqueous colloidal dispersion of claim 13 comprising emulsion polymerizing the monomeric system thereof at a pH of from about 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 18

A process for making the aqueous colloidal dispersion of claim 14 comprising emulsion polymerizing the monomeric system thereof at a pH of from about 2.5 to about 5 in the presence of a free radical producing initiator at a temperature of from about 75° to about 85° C.

Claim 19

A thickened aqueous composition containing an effective thickening amount of at least a partially neutralized emulsion copolymer of claim 6.

Claim 20

A process for making a thickened aqueous composition which comprises combining with the aqueous composition an effective thickening amount of an emulsion copolymer of claim 6 and at least partially neutralizing said copolymer to thus thicken said composition.

Claim 21

A thickened composition according to claim 17 comprising a latex paint.

Claim 22

A thickened composition according to claim 17 comprising a pigment dispersion.

Claim 23

A thickened composition according to claim 17 comprising an oil well drilling fluid.

Claim 24

A thickened composition according to claim 17 comprising a textile printing paste.

Claim 25

A thickened composition according to claim 17 comprising an adhesive.

Claim 26

A thickened composition according to claim 17 comprising a liquid detergent.

Claim 27

A thickened composition according to claim 17 comprising a paper coating composition.

Claim 28

A thickened composition according to claim 17 comprising a wall joint compound.