Copolymers of alkyl poly(oxyalkylene) itaconates and thickening processes using them

Claim 2

A copolymer obtained by copolymerization of a monomer system comprising (1) 0.5 to 30 weight percent of at least one monomer of the formula wherein R 1 and R 2 , are the same or different and represent hydrogen, alkyl, alkylaryl and polycyclic alkyl groups having 1 to 30 carbon atoms; - m, m', n, n', are the same or different and are zero or an average number of up to 60 or more, provided that at least one of m and n is at least 2 and provided that the R 1 or R 2 group, when m or n, respectively, is at least 2, is one of said alkyl, alkylaryl and polycyclic alkyl groups having at. least 8 carbon atoms; R' is C 1 -C 2 alkyl; and the expressions [(CH 2 CH 2 O) m (CHR'CH 2 O) m ,] R1 and [(CH 2 CH 2 O) n (CHR'CH 2 O) n ,]R 2 denote that the groups (CH 2 CH 2 O) m and (CHR'CH20)m, and the groups (CH 2 CH 2 O) n and (CHR'CH 2 O) n " respectively, may be present in any random order or may be present in the exact order (CH 2 CH 2 O) m (CHR'-CH 2 O) m , R 1 or (CH 2 CH 2 O) n (CHR' CH 2 O) n , R 2 ; and (2) at least 10 weight percent of copolymerizable ethylenically unsaturated monomer or monomer mixture comprising methacrylic acid, acrylic acid, itaconic acid, acryloxypropionic acid, maleic acid, fumaric acid, citraconic acid and/or crotonic acid; (3) optionally at least one compound of the formula H 2 C=CYZ wherein (a) Y is H and Z is COOR", C 6 H 4 R''', CN, Cl, OC(O) R' ' ' ' , CONH 2 or CH = CH 2 ; (b) Y is C l -C 4 alkyl and Z is COOR" , C 6 H 4 R''', CN, CONH 2 , or CH=CH 2 ; or (c) Y and Z are Cl; and R'' is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl or lower alkoxy (C 2 -C 8 ) alkyl; R''' is H, Cl, Br or C 1 -C 4 alkyl; and R'''' is C l -C 8 alkyl; and (4) zero to 1.0 weight percent of polyethylenically unsaturated monomer(s).

Claim 3

Polymer of claim 1 wherein the amount of component (1) in the monomer system is 0.5 to 25 percent by weight.

Claim 4

Polymer of any preceding claim wherein the amount of component (2) in the monomer system is 10 to 70 percent by weight.

Claim 5

Polymer of any preceding claim wherein monomer (2) comprises methacrylic acid, acrylic acid, acryloxypropionic acid and/or itaconic acid preferably acrylic acid, methacrylic acid, and/or itaconic acid.

Claim 6

Polymer of any preceding claim wherein monomer (1) comprises mono- or di-ester of itaconic acid wherein at least one of the two itaconic acid carboxy groups is esterified by a C 8 -C 30 hydrocarbyl poly(oxyethylene) group, the poly(oxyethylene) moiety being at least two oxyethylene groups; preferably di-ester of itaconic acid wherein the two itaconic acid carboxy groups are each esterified by a C 12 -C 18 hydrocarbyl poly(oxyethylene) group, the poly(oxyethylene) moiety being at least two oxyethylene groups or comprises monomer of the formula in which R 1 , m , n and R 2 are as defined in claim 1.

Claim 7

Polymer of any preceding claim wherein the amount of monomer (3) in the monomer system is at least 25 percent by weight and the monomer (3) preferably comprises at least one of the copolymerizable ethylenically unsaturated comonomers: C 1 -C 8 alkyl, C 2 -C a hydroxyalkyl and lower alkoxytC 2 -C 8 )alkyl acrylates, methacrylates, and 1-alkenoates containing four to six carbons in the alkene-carbon chain; styrene and vinyl [(C 1 -C 8 )alkyl]benzene, and [(C 1 -C 8 )alkylphenoxy]alkees containing three to six carbons in the alkene-carbon chain, acrylonitrile, methacrylonitrile, and cyanoalkenes containing four to six carbons in the alkene-carbon chain; vinyl and vinylidene chloride; vinyl esters of C 2 -C 9 saturated aliphatic carboxylic acids; and polyethylenically unsaturated monomers.

Claim 8

Polymer of any preceding claim wherein monomer (3) comprises at least one (C 1 -C 4 )-alkyl acrylate and/or methacrylate.

Claim 9

Polymer of any of claims 2 to 7 wherein the total of the percentage of monomers (1), (2), (3) and (4) is 100.

Claim 10

Polymer of any preceding claim obtained by aqueous emulsion copolymerization of a monomer system comprising (1) 30 to 45 weight percent of methacrylic acid; (2) 1 to 15 weight percent of di-ester of itaconic acid wherein the two itaconic acid carboxy groups are each esterified by a C 12 - C 18 hydrocarbyl poly(oxyethylene) group, the average value of the number of oxyethylene groups in each poly (oxyethylene) chain being at least 10; and (3) 40 to 60 weight percent of ethyl acrylate.

Claim 11

A process of thickening an aqueous system comprising adding to the system polymer of any preceding claim and, optionally at least partially neutralizing said polymer.

Claim 12

A process as claimed in claim 10 in which the polymer is added in aqueous dispersion.

Claim 13

A process as claimed in claim 11 wherein the aqueous system comprises a water-based paint composition comprising an aqueous dispersion of vinyl addition emulsion polymer as a binder and pigment in a pigment volume concentration of up to 65%.

Claim 14

A process as claimed in claim 10 or 11 which comprises adding to the aqueous system surfactant in an amount effective to provide thickening beyond the thickening provided by at least partial neutralization of said polymer, the surfactant preferably being anionic or nonionic.

Claim 15

A process as claimed in claim 10 or 11 or claim 13 as dependent on claim 10 or 11 wherein the aqueous system comprises an aqueous pigment dispersion, an oil-well drilling fluid, a textile printing paste, a dentrifice composition or a liquid detergent composition.

Claim 16

A process as claimed in claim 12 in which the vinyl addition emulsion polymer binder comprises vinyl acetate polymer, acrylic acid ester polymer, methacrylic acid ester polymer, styrene-butadiene polymer, vinyl acetate/acrylic acid ester copolymer, vinyl acetate/methacrylic acid ester copolymer, vinyl acetate/acrylic acid ester/methacrylic acid ester copolymer and/or acrylic acid ester/methacrylic acid ester copolymer, the paint composition also containing at least partially neutralized emulsion polymer of any of claims 1 to 9 to control the rheological properties of the paint.

Claim 17

A process as claimed in claim 10 wherein the aqueous system comprises a water-in-oil clear concentrate containing surfactant, preferably sorbitan mono-oleate, dissolved in hydrocarbon distillate, preferably mineral spirits having a flash point over 120°C, wherein the thickening polymer comprise.s an aqueous dispersion of polymer of any of claims 1 to 9 wherein monomer '(2) comprises acrylic and/or methacrylic acid, said thickening polymer being thickened by at least partial neutralization by a base, preferably ammonium hydroxide, the resulting concentrate being dilutable with water to form a printing clear which can be mixed with aqueous vinyl addition emulsion polymer to serve as a binder and optionally with color concentrate to form a pigment printing paste for pigment printing and dying of textiles.

Claim 18

Process as claimed in claim 16 wherein the aqueous system comprises a water-in-oil clear concentrate as defined in claim 20, additional water, an aqueous dispersion of a binder comprising vinyl addition emulsion polymer having a hert-reactive component therein and a color concentrate, the several components being mixed to form a pigment paste having desired rheological properties suitable for the pigment printing and dying of textiles.

Claim 19

A process for making a copolymer which comprises polymerising a monomer system comprising (1) 0.5 to 30 weight percent of at least one monomer of the formula 1 2 wherein R and R 2 , are the same or different and represent hydrogen, alkyl, alkylaryl and polycyclic alkyl groups having 1 to 30 carbon atoms; m, m', n, n', are the same or different and are zero or. an average number of up to 60 or more, provided that at least one of m and n is at least 2 and provided that the R 1 or R 2 group, when m or n, respectively, is at least 2, is one of said alkyl, alkylaryl and polycyclic alkyl groups having at least 8 carbon atoms; R ' is C 1 -C 2 alkyl; and the expressions [(CH 2 CH 2 O) m (CHR' CH 2 O) m ,] R 1 and [(CH 2 CH 2 O) n (CHR'CH 2 O) n ,]R 2 denote that the groups ( CH 2 CH 2 0) m and (CHR'CH 2 O) m , and the groups (CH 2 CH 2 O) n and (CHR'CH 2 O)n" respectively, may be present in any random order or may be present in the exact order (CH 2 CH 2 O) m (CHR' CH 2 O) m , R 1 or (CH 2 CH 2 O) n (CHR' CH 2 O) n , R 2 ' and (2) at least 10 weight percent of copolymerizable ethylenically unsaturated monomer or monomer mixture comprising methacrylic acid, acrylic acid, itaconic acid, acryloxypropionic acid, maleic acid, fumaric arid, citraconic acid and/or crotonic acid; (3) optionally at least one compound of the formula H 2 C=CYZ wherein (a) Y is H and Z is COOR'' , C 6 H 4 R''', CN, Cl, OC(O)R'''', CONH 2 or CH=CH 2 ; (b) Y is C l -C 4 alkyl and Z is COOR'' , C 6 H 4 R''', CN, CONH 2 , or CH=CH 2 ; or (c) Y and Z are Cl; and R'' is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl or lower alkoxy(C 2 -C 8 )alkyl; R''' is H, Cl, Br or C 1 -C 4 alkyl; and Ris C 1 -C 8 alkyl; and (4) zero to 1.0 weight percent of polyethylenically unsaturated monomer(s).

Claim 20

A process for making a copolymer which comprises polymerising a monomer system comprising (1) 0.5 to 30 weight percent of at least one monomer of the formula 1 2 wherein R and R 2 , are the same or different and represent hydrogen, alkyl, alkylaryl and polycyclic alkyl groups having 1 to 30 carbon atoms; m, m', n, n', are the same or different and are zero or. an average number of up to 60 or more, provided that at least one of m and n is at least 2 and provided that the R 1 or R 2 group, when m or n, respectively, is at least 2, is one of said alkyl, alkylaryl and polycyclic alkyl groups having at least 8 carbon atoms; R ' is C 1 -C 2 alkyl; and the expressions [(CH 2 CH 2 O) m (CHR' CH 2 O) m ,] R 1 and [(CH 2 CH 2 O) n (CHR'CH 2 O) n ,]R 2 denote that the groups ( CH 2 CH 2 0) m and (CHR'CH 2 O) m , and the groups (CH 2 CH 2 O) n and (CHR'CH 2 O)n" respectively, may be present in any random order or may be present in the exact order (CH 2 CH 2 O) m (CHR' CH 2 O) m , R 1 or (CH 2 CH 2 O) n (CHR' CH 2 O) n , R 2 ' and (2) at least 10 weight percent of copolymerizable ethylenically unsaturated monomer or monomer mixture comprising methacrylic acid, acrylic acid, itaconic acid, acryloxypropionic acid, maleic acid, fumaric arid, citraconic acid and/or crotonic acid; (3) optionally at least one compound of the formula H 2 C=CYZ wherein (a) Y is H and Z is COOR'' , C 6 H 4 R''', CN, Cl, OC(O)R'''', CONH 2 or CH=CH 2 ; (b) Y is C l -C 4 alkyl and Z is COOR'' , C 6 H 4 R''', CN, CONH 2 , or CH=CH 2 ; or (c) Y and Z are Cl; and R'' is C 1 -C 8 alkyl or C 2 -C 8 hydroxyalkyl or lower alkoxy(C 2 -C 8 )alkyl; R''' is H, Cl, Br or C 1 -C 4 alkyl; and Ris C 1 -C 8 alkyl; and (4) zero to 1.0 weight percent of polyethylenically unsaturated monomer(s).

Claim 21

Process of claim 1 wherein the amount of component (I) in the monomer system is 0.5 to 25 percent by weight.

Claim 22

Process of any preceding claim wherein the amount of component (2) in the monomer system is 10 to 70 percent by weight.

Claim 23

Process of any preceding claim wherein monomer (2) comprises methacrylic acid, acrylic acid, acryloxypropionic acid and/or itaconic acid preferably acrylic acid, methacrylic acid, and/or itaconic acid.

Claim 24

Process of any preceding claim wherein monomer (1) comprises mono- or di-ester of itaconic acid wherein at least one of the two itaconic acid carboxy groups is esterified by a C 8 -C 30 -hydrocarbyl poly(oxyethylene) group, the poly(oxyethylene) moiety being at least two oxyethylene groups; preferably di-ester of itaconic acid wherein the two itaconic acid carboxy groups are each esterified by a C 12 -C 18 hydrocarbyl poly(oxyethylene) group, the poly(oxyethylene) moiety being at least two oxyethylene groups or comprises monomer of the formula in which R 1 , m, n and R 2 are as defined in claim 1.

Claim 25

Process of any preceding claim wherein the amount of monomer (3) in the monomer system is at least 25 percent by weight and the monomer (3) preferably comprises at least one of the copolymerizable ethylenically unsaturated comonomers: C 1 -C 8 alkyl, C 2 -C 8 hydroxyalkyl and lower alkoxy(C 2 -C 8 )alkyl acrylates, methacrylates, and 1-alkenoates containing four to six carbons in the alkene-carbon chain; styrene and vinyl [(C 1 -C 8 ) lkyl] benzene, and [(C 1 -C 8 )alkylphenoxy] alkenes containing three to six carbons in the alkene-carbon chain, acrylonitrile, methacrylonitrile, and cyanoalkenes containing four to six carbons in the alkene-carbon chain; vinyl and vinylidene chloride; vinyl esters of C 2 -C 9 saturated aliphatic carboxylic acids; and polyethylenically unsaturated monomers.

Claim 26

Process of any preceding claim wherein monomer (3) comprises at least one (C l -C 4 )-alkyl acrylate and/or methacrylate.

Claim 27

Process of any of claims 2 to 7 wherein the total of the percentage of monomers (1), (2), (3) and (4) is 100.

Claim 28

Process of any preceding claim which comprises aqueous emulsion copolymerization of a monomer system comprising (1) 30 to 45 weight percent of methacrylic acid; (2) 1 to 15 weight percent of di-ester of itaconic acid wherein the two itaconic acid carboxy groups are each esterified by a C12-C18 hydrocarbyl poly(oxyethylene) group, the average value of the number of oxyethylene groups in each poly(oxyethylene) chain being at least 10; and (3) 40 to 60 weight percent of ethyl acrylate.

Claim 29

A process of thickening an aqueous system comprising adding to the system polymer made by a process of any preceding claim and, optionally at least partially neutralizing said polymer.

Claim 30

A process as claimed in claim 10 in which the polymer is added in aqueous dispersion.

Claim 31

A process as claimed in claim 11 wherein the aqueous system comprises a water-based paint composition comprising an aqueous dispersion of vinyl addition emulsion polymer as a binder and pigment in a pigment volume concentration of up to 65%.

Claim 32

A process as claimed in claim 10 or 11 which comprises adding to the aqueous system surfactant in an amount effective to provide thickening beyond the thickening provided by at least partial neutralization of said polymer, the surfactant preferably being anionic or nonionic.

Claim 33

A process as claimed in claim 10 or 11 or claim 13 as dependent on claim 10 or 11 wherein the aqueous system comprises an aqueous pigment dispersion, an oil-well drilling fluid, a textile printing paste, a dentrifice composition or a liquid detergent composition.

Claim 34

A process as claimed in claim 12 in which the vinyl addition emulsion polymer binder comprises vinyl acetate polymer, acrylic acid ester polymer, methacrylic acid ester polymer, styrene-butadiene polymer, vinyl acetate/acrylic acid ester copolymer, vinyl acetate/methacrylic acid ester copolymer, vinyl acetate/acrylic acid ester/methacrylic acid ester copolymer and/or acrylic acid ester/methacrylic acid ester copolymer, the paint composition also containing at least partially neutralized emulsion polymer of any of claims 1 to 9 to control the rheological properties of the paint.

Claim 35

A process as claimed in claim 10 wherein the aqueous system comprises a water-in-oil clear concentrate containing surfactant, preferably sorbitan mono-oleate, dissolved in hydrocarbon distillate, preferably mineral spirits having a -flash point over 120°C, wherein the thickening polymer . comprises an aqueous dispersion of polymer of any of claims 1 to 9 wherein monomer (2) comprises acrylic and/or methacrylic acid, said thickening polymer being thickened by at least partial neutralization by a base, preferably ammonium hydroxide, the resulting concentrate being dilutable with water to form a printing clear which can be mixed with aqueous vinyl addition emulsion polymer to serve as a binder and optionally with color concentrate to form a pigment printing paste for pigment printing and dying of textiles.

Claim 36

Process as claimed in claim 16 wherein the aqueous system comprises a water-in-oil clear concentrate as defined in claim 20, additional water, an aqueous dispersion of a binder comprising vinyl addition emulsion polymer having a hert-reactive component therein and a color concentrate, the several components being mixed to form a pigment paste having desired rheological properties suitable for the pigment printing and dying of textiles.