Tri-substituted aromatic-containing monomers, copolymers and methods for use
View Patent ↗Disclosed are novel tri-substituted aromatic-alkoxylated monomers, polymers made with the novel tri-substituted aromatic-alkoxylated monomers, pH responsive polymers made with the novel tri-substituted aromatic-alkoxylated monomers, and related methods. Also disclosed is an aqueous coating composition including at least one latex polymer derived from at least one monomer copolymerized or blended with alkali swellable acrylate copolymer. Also provided is a method of preparing an aqueous coating composition such as a latex paint including the above components.
1. An ethylenically unsaturated monomer according to structure (D.I):
R 18 -R 14 -R 13 -R 12 -R 11 (D.I).
R 12 is absent or is a bivalent linking group,
R 13 is bivalent polyether group,
R 14 is absent or is a bivalent linking group;
R 18 is a moiety having a site of ethylenic unsaturation; and
R 11 is a tri-substituted aromatic group according to the structure D.XII
wherein R 1 , R 2 and R 3 are independently selected from the following structures D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId:
or a C 9 -C 30 branched or linear alkyl group or alkenyl group;
wherein at least one of R 1 , R 2 and R 3 is the C 9 -C 30 branched or linear alkyl group or alkenyl group, and at least one of R 1 , R 2 and R 3 is selected from structure D.XIIIa, D.XIIIb, D.XIIIc, or D.XIIId.
2. The ethylenically unsaturated monomer of claim 1 wherein R 13 is —[CH(R 20 )CH(R 21 )O] x —, wherein x is an integer of from 0 to 100, and R 20 and R 21 are independently selected from any of the following:
H; —CH 2 OH; phenyl; —CH 2 Cl;
a C 1 -C 30 straight or branched alkyl or alkenyl;
—CH 2 OR 22 wherein R 22 is C 1 -C 30 straight or branched alkyl or alkenyl, phenyl, or alkyl substituted phenyl; or
R′COOCH 2 — where R′ is C 1 -C 30 straight or branched alkyl or alkenyl.
3. The ethylenically unsaturated monomer of claim 1 wherein the monomer is according to structure D.XXX:
wherein:
g is an integer from 2 to 4;
h is an integer from 2 to 4;
b is an integer from 0 to 1;
k is an integer from 0 to 100;
i is an integer from 0 to 40;
j is an integer from 0 to 40;
R 18 is a moiety having a site of ethylenic unsaturation;
R 11 is according to structure D.XII
wherein R 1 , R 2 and R 3 are independently selected from the following structures D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId:
or a C 9 -C 30 branched or linear alkyl group or alkenyl group;
wherein at least one of R 1 , R 2 and R 3 is the C 9 -C 30 branched or alkyl group or alkenyl group and at least one of R 1 , R 2 and R 3 is selected from D.XIIIa, D.XIIIb, D.XIIIc, or D.XIIId.
4. The monomer of claim 3 wherein R 18 is according to structure (D.XV):
wherein R 19 is H or (C 1 -C 4 )alkyl.
5. The monomer of claim 1 wherein the C 9 -C 30 branched or linear alkyl group or alkenyl group is a C 10 -C 30 branched or linear alkyl group.
6. The monomer of claim 1 wherein the C 9 -C 30 branched or linear alkyl group or alkenyl group is a C 10 -C 24 branched or linear alkenyl group.
7. The monomer of claim 1 wherein the C 9 -C 30 branched or linear alkyl group or alkenyl group is a C 9 -C 14 branched or linear alkenyl group.
8. The monomer of claim 1 wherein the C 9 -C 30 branched or linear alkyl group or alkenyl group is a C 23 -C 30 branched or linear alkenyl group.
9. The monomer of claim 1 wherein R 11 is a tri-substituted aromatic group according to the structure D.XII
wherein R 1 , R 2 and R 3 are independently selected from:
a styryl group, or
a C 9 -C 30 branched or linear alkyl group or alkenyl group;
wherein at least one of R 1 , R 2 and R 3 is the C 9 -C 30 branched or linear alkyl group or alkenyl group, and at least one of R 1 , R 2 and R 3 is the styryl group.
10. The monomer of claim 1 wherein R 11 is a tri-substituted aromatic group according to the structure D.XII-1
wherein R 1 , is the C 9 -C 30 branched or linear alkyl group or alkenyl group.
11. The monomer of claim 10 wherein the C 9 -C 30 branched or linear alkyl group or alkenyl group is a C 9 -C 14 branched or linear alkyl group or alkenyl group.
12. A copolymer comprising at least one monomer according to structure D.XVI:
wherein:
g is an integer from 2 to 4;
h is an integer from 2 to 4;
b is an integer from 0 to 1;
k is an integer from 0 to 25;
i is an integer from 0 to 40;
j is an integer from 0 to 40;
R 19 is hydrogen; methyl or ethyl;
R 11 is according to structure D.XII
wherein R 1 , R 2 and R 3 are independently selected from the following structures D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId:
or a C 9 -C 30 branched or linear alkyl group or alkenyl group;
wherein at least one of R 1 , R 2 and R 3 is the C 9 -C 30 branched or linear alkyl group or alkenyl group and at least one of R 1 , R 2 and R 3 is selected from structure D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId.
13. A pH responsive copolymer of unsaturated copolymerizable monomers, said unsaturated copolymerizable monomers comprising, based on total weight of monomers:
A. about 0-60 weight percent of at least one C 3 -C 8 alpha beta- ethylenically unsaturated acidic monomer, preferably a C 3 -C 8 alpha beta-ethylenically unsaturated carboxylic acid monomer;
B. about 15-70 weight percent of at least one nonionic, copolymerizable C 2 -C 12 alpha, beta-ethylenically unsaturated monomer; and
C. about 0.05 to 30 weight percent of at least one nonionic ethylenically unsaturated hydrophobic monomer according to claim 1 .
14. The pH responsive copolymer of claim 13 , comprising, based on total weight of monomers:
A. about 5 to 60 weight percent of the at least one C 3 -C 8 alpha beta-ethylenically unsaturated acidic monomer, preferably a C 3 -C 8 alpha beta-ethylenically unsaturated carboxylic acid monomer;
B. about 15-70 weight percent of the at least one non-ionic, copolymerizable C 2 -C 12 alpha, beta-ethylenically unsaturated monomer; and
C. about 0.05 to 30 weight percent of the at least one ethylenically unsaturated hydrophobic monomer according to structure D.XVI:
wherein:
g is an integer from 2 to 4;
h is an integer from 2 to 4;
b is an integer from 0 to 1;
k is an integer from 0 to 25;
i is an integer from 0 to 40;
j is an integer from 0 to 40;
R 19 is hydrogen; methyl or ethyl;
R 11 is a tri-substituted aromatic group according to the structure D.XII
wherein R 1 , R 2 and R 3 are independently selected from the following structures D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId:
or a C 2 -C 30 branched or linear alkyl group or alkenyl group;
wherein at least one of R 1 , R 2 and R 3 is the C 2 -C 30 branched or linear alkyl group or
alkenyl group and at least one of R 1 , R 2 and R 3 is selected from structure D.XIIIa, D.XIIIb, D.XIIIc, D.XIIId.
15. The copolymer of claim 14 , wherein the carboxylic acid monomer (A) is present from about 25 weight percent to about 60 weight percent based on total monomer weight.
16. The copolymer of claim 14 , wherein the carboxylic acid monomer (A) is selected from a group consisting of methacrylic acid, acrylic acid and a combination thereof.
17. The copolymer of claim 14 , wherein the nonionic monomer (B) is alkyl acrylate.
18. An aqueous composition, comprising water and the pH responsive copolymer of claim 14 .
19. A method for thickening an aqueous emulsion, comprising: forming a blend by blending with the aqueous emulsion an amount of the pH-responsive composition of claim 17 , effective to thicken the aqueous emulsion when pH of the blend is adjusted to a pH in the range of about 6.5 to about 11.