Surfactant-compatible star macromolecules

1. A surfactant-system thickening macromolecule is represented by Formula B:

wherein:

Core represents a crosslinked polymeric segment;

P1 independently represents the hydrophilic polymeric segment of the at least first polymeric arm comprised of monomeric residues of polymerized hydrophilic monomers;

P2 independently represents the further segment of the at least second polymeric arm comprised of at least one monomeric residue of a polymerized surfactant-system thickening monomer comprising a C 6 or greater alkyl acrylate; C 6 or greater alkenyl acrylate; C 6 or greater alkyl alkyl acrylate; C 6 or greater alkenyl alkyl acrylate; C 6 or greater alkyl acrylamide; C 6 or greater alkenyl acrylamide; C 6 or greater alkyl alkyl acrylamide; C 6 or greater alkenyl alkyl acrylamide; C 2 or greater alkyl vinyl ether; C 2 or greater alkenyl vinyl ether; C 1 or greater alkyl allyl ether; or C 1 or greater alkenyl allyl ether;

P3 independently represents the hydrophilic polymeric segment of the at least second polymeric arm comprised of monomeric residues of polymerized hydrophilic monomers;

P4 independently represents the hydrophobic polymeric segment of the at least third polymeric arm comprised of monomeric residues of polymerized hydrophobic monomers;

P5 independently represents the hydrophilic polymeric segment of the at least third polymeric arm comprised of monomeric residues of polymerized hydrophilic monomers;

q1 independently represents the number of monomeric residues in P1 and has a value in the range of between 5 to 2000;

q2 independently represents the number of monomeric residues in P2 and has a value in the range of between 1 to 500;

q3 independently represents the number of monomeric residues in P3 and has a value in the range of between 10 to 5000;

q4 independently represents the number of monomeric residues in P4 and has a value in the range of between 1 to 500;

q5 independently represents the number of monomeric residues in P5 and has a value in the range of between 10 to 5000;

r independently represents the number of the at least first polymeric arms covalently attached to the Core and has a value in the range of between 1 to 1000;

s independently represents the number of the at least second polymeric arms covalently attached to the Core and has a value in the range of between 1 to 1000; and

t independently represents the number of the at least third polymeric arms covalently attached to the Core and has a value in the range of between 1 to 1000.

2. The macromolecule of claim 1 , wherein a portion of the further segment is represented by Formula E:

wherein:

R 11 , R 12 , R 13 independently represent hydrogen, methyl, ethyl, or C 3-18 alkyl; wherein the alkyl may be branched or unbranched, linear or cyclic, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 14 independently represents C 1-12 hydrocarbyl, —C 1-12 hydrocarbyl-(O—C 1-6 hydrocarbyl) w , —C 1-12 hydrocarbyl-((CO)O—C 1-6 hydrocarbyl) w , —C 1-12 hydrocarbyl-((CO)NH—C 1-6 hydrocarbyl) w ; wherein each hydrocarbyl portion independently may be branched or unbranched, linear or cyclic, saturated (alkyl) or unsaturated (alkenyl), and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 15 independently represents C 13-40 hydrocarbyl, —C 13-40 hydrocarbyl-(O—C 1-6 hydrocarbyl) w , —C 13-40 hydrocarbyl-((CO)O—C 1-6 hydrocarbyl) w , C 13-40 hydrocarbyl-((CO)NH—C 1-6 alkyl) w ; wherein each hydrocarbyl portion independently may be branched or unbranched, linear or cyclic, saturated (alkyl) or unsaturated (alkenyl), and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol); or a hydrophobic moiety of a surfactant, a hydrophobic moiety of a lipid, or a hydrophobic moiety of a fatty alcohol;

Y represents a covalent bond, ethylene glycol, poly(ethylene glycol), polyether, polyamide, C 1-6 alkyl, or combinations thereof, or is independently absent;

m independently represents a value in the range of 1-500;

n independently represents a value in the range of 1-500; and

w independently represents a value in the range of 1-1000.

3. The macromolecule of claim 1 , wherein the surfactant-system thickening macromolecule has a molecular weight (Mn) in the range of between 5,000 g/mol and 10,000,000 g/mol.

4. The macromolecule of claim 1 , wherein the molecular weight (Mn) of the at least one polymeric arm is between 1,000 g/mol to 250,000 g/mol.

5. The macromolecule of claim 1 , wherein when 0.4 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 5,000 cP at a shear rate of 2.2 s −1 at 25° C., according to the Thickening and Shear Thinning in Water Test.

6. The macromolecule of claim 1 , wherein when 2.0 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 500 cP at a shear rate of 2.2 s −1 at 25° C., according to the SLES Surfactant Compatibility Test.

7. The macromolecule of claim 1 , wherein when 2.0 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 5,000 cP at a shear rate of 2.2 s −1 at 25° C., according to the Hybrid SLES-CH Surfactant Compatibility Test.

8. The macromolecule of claim 1 , wherein when 1.5 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 2,000 cP at a shear rate of 2.2 s −1 at 25° C., according to the Hybrid CB-SLES Surfactant Compatibility Test.

9. The macromolecule of claim 1 , wherein when 1.5 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 2,000 cP at a shear rate of 0.22 s −1 at 25° C., according to the Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

10. The macromolecule of claim 1 , wherein when 2.0 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 15,000 cP at a shear rate of 2.2 s −1 at 25° C., according to the Ritabate 20 Surfactant Compatibility Test.

11. The macromolecule of claim 1 , wherein when 2.0 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 1,500 cP at a shear rate of 2.2 s −1 at 25° C., according to the APG Surfactant Compatibility Test.

12. The macromolecule of claim 1 , wherein when 0.4 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 100,000 cP at a shear rate of 0.22 s −1 at 25° C., and has a Dynamic Viscosity at 80° C. that is at least 50% relative to the viscosity of the gel at 25° C., according to the Temperature Stability Test.

13. The macromolecule of claim 1 , wherein when 1.5 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 8,000 cP at an adjusted pH in the range of between 4.5 to 6.5 at a shear rate of 0.22 s −1 at 25° C., according to the pH Efficiency Range in Hybrid CB/SLES Surfactant Test.

14. The macromolecule of claim 1 , wherein when 0.4 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamic viscosity of at least 5,000 cP at an adjusted pH in the range of between 5 to 12 at a shear rate of 0.22 s −1 at 25° C., according to the pH Efficiency Range Test.

15. A surfactant-modified star macromolecule, comprising:

i) a core;

ii) at least one first polymeric arm, comprising a hydrophilic polymeric segment covalently attached to the core; and

iii) at least one second polymeric arm, comprising:

a) a hydrophilic polymeric segment covalently attached to the core; and

b) a further segment comprising at least one pendant moiety represented by

[L 1 —G 1 —L 2 —G 2 ];

wherein:

G1 independently represents a residue of a hydrophilic moiety of the surfactant;

G2 independently represents a residue of a hydrophobic moiety of the surfactant;

L1 independently represents a linking group or a covalent bond, attaching G1 to the further segment; and

L2 independently represents a linking group or a covalent bond, linking G1 and G2.

16. A method of increasing the viscosity of a surfactant-containing aqueous system, comprising: introducing the surfactant-system thickening macromolecule of claim 1 into the surfactant-containing aqueous system.

17. A method of increasing the viscosity of a surfactant-containing aqueous system, comprising: introducing the surfactant-modified star macromolecule of claim 15 into the surfactant-containing aqueous system.

18. A method of increasing the viscosity of a surfactant-containing aqueous system, comprising:

introducing a surfactant-system thickening macromolecule into the surfactant-containing aqueous system, wherein the surfactant-system thickening macromolecule comprises:

i) a core;

ii) at least one first polymeric arm, comprising a polymeric segment comprised of monomeric residues of polymerized hydrophilic monomers; and

iii) at least one second polymeric arm, comprises:

1) at least one pendant micelle-philic moiety; or

2) a polymeric segment comprised of at least one monomeric residue of a polymerized micelle-philic monomer.

19. The method of claim 18 , wherein the at least one pendant micelle-philic moiety is represented by the formula:

[L 1 —G 1 —L 2 —G 2 ]

wherein:

G 1 independently represents a residue of a hydrophilic moiety of the surfactant;

G 2 independently represents a residue of a hydrophobic moiety of the surfactant;

L 1 independently represents a linking group or a covalent bond, attaching G 1 to the at least one second polymeric arm; and

L 2 independently represents a linking group or a covalent bond, linking G 1 and G 2 .

20. The method of claim 18 , wherein the at least one pendant micelle-philic moiety or the at least one monomeric residue of a polymerized micelle-philic monomer comprises a C6 or greater alkyl moiety, a fluorine-modified C4 or greater alkyl moiety, or a C6 or greater alkenyl moiety.

21. The method of claim 18 , wherein the micelle-philic monomer is represented by Formula I-V:

wherein:

R 1 , R 2 , and R 3 independently represent hydrogen, methyl, ethyl, or C 3-18 alkyl; wherein the alkyl may be branched or unbranched, linear or cyclic, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 4 and R 7 independently represent C 13 or greater alkyl, —C 6 or greater alkyl-(O—C 1-6 alkyl) n , C 6 or greater alkenyl, or C 6 or greater alkenyl-(O—C 1-6 alkyl) n ; or when R 3 is C 1 or greater, then R 4 may independently represent C 11 or greater alkyl, —C 6 or greater alkyl —(O—C 1-6 alkyl) n , C 6 or greater alkenyl, or C 6 or greater alkenyl-(O—C 1-6 alkyl) n ; wherein each alkyl portion independently may be branched or unbranched, linear or cyclic, saturated or unsaturated, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 5 independently represents C 19 or greater alkyl, —C 6 or greater alkyl —(O—C 1-6 alkyl) n , C 6 or greater alkenyl, or C 6 or greater alkenyl-(O—C 1-6 alkyl) n ; or when R 6 is C 1 or greater, then R 5 may independently represent C 13 or greater alkyl, —C 6 or greater alkyl —(O—C 1-6 alkyl) n , C 6 or greater alkenyl, or C 6 or greater alkenyl-(O—C 1-6 alkyl) n ; wherein each alkyl portion independently may be branched or unbranched, linear or cyclic, saturated or unsaturated, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 6 independently represents hydrogen, C 1-18 alkyl, —C 1-18 alkyl-(O—C 1-6 alkyl) n , or is R 4 , or is R 5 ; wherein each alkyl portion independently may be branched or unbranched, linear or cyclic, saturated or unsaturated, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 8 independently represents C 2 or greater alkyl, —C 2 or greater alkyl-(O—C 1-6 alkyl) n , C 3 or greater alkenyl, —C 3 or greater alkenyl-(O—C 1-6 alkyl) n ; wherein each alkyl portion independently may be branched or unbranched, linear or cyclic, saturated or unsaturated, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

R 9 independently represents C 1 or greater alkyl, —C 1 or greater alkyl-(O—C 1-6 alkyl) n , C 3 or greater alkenyl, —C 3 or greater alkenyl-(O—C 1-6 alkyl) n ; wherein each alkyl portion independently may be branched or unbranched, linear or cyclic, saturated or unsaturated, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol); or

R 4 , R 5 , R 7 , R 8 , R 9 independently represent a hydrophobic portion of a surfactant, a hydrophobic portion of a lipid, or a hydrophobic portion of a fatty alcohol;

A 1 , A 2 , A 3 and A 4 independently represent CH, CR 10 , or N, wherein at least two of A 1 , A 2 , A 3 and A 4 is CH or CR 10 ;

R 10 independently represents hydrogen, C 1-10 alkyl, halogen, hydroxyl, C 1-10 alkoxy; wherein the alkyl or alkoxy may be branched or unbranched, linear or cyclic, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol);

Y independently represents a covalent bond, —O—, —S—, —N(H)—, —N(R 1 )—, —(CO)—, —S(O)—, —S(O) 2 —, —S(O) 2 N(R 1 )—, —(CO)N(R 1 )—, —N(R 1 )—(CO)—, —(CO)O—, or —O—(CO)—;

L 1 independently represents a covalent bond, ethylene glycol, poly(ethylene glycol), polyether, polyamide, C 1-6 alkyl, —(CO)N(R 1 )—, —N(R 1 )—(CO)—, —(CO)O—, —O—(CO)—, or combinations thereof, or is independently absent; or

L 1 independently represents a hydrophilic portion of a surfactant, a hydrophilic portion of a lipid, or a hydrophilic portion of a fatty alcohol;

L 2 independently represents (CH 2 ) 1-40 , C 1-40 alkyl, (O—C 2-6 alkyl) n , or (C 2-6 alkyl)-(O—C 2-6 alkyl) n ; wherein the alkyl may be branched or unbranched, linear or cyclic, and may be optionally substituted with one or more halogens, C 1-6 alkoxy groups, or poly(ethylene glycol); and

n independently represents a value in the range of 1-1000.

22. The method of claim 18 , wherein the surfactant is a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, or a cationic surfactant.

23. The macromolecule of claim 1 , wherein the further segment of P2comprises polymerized methacrylate monomers.

24. The macromolecule of claim 23 , wherein the polymerized methacrylate monomers comprise a polymerized mixture of stearyl methacrylate and methyl methacrylate.

25. The macromolecule of claim 1 , wherein:

the crosslinked polymeric segment of the Core comprises polymerized trimethylolpropane triacrylate;

the hydrophilic polymeric segments of P1, P3, and P5 each independently comprise polymerized acrylic acid;

the further segment of P2 comprises a polymerized mixture of stearyl methacrylate and methyl methacrylate; and

the hydrophobic polymeric segment of P4 comprises polymerized methyl methacrylate.

26. The macromolecule of claim 25 , wherein:

q1 is about 50 to about 250;

q2 is about 20 to about 30;

q3 is about 200 to about 400;

q4 is about 10 to about 30;

r is about 2 to about 8;

s is about 1 to about 6; and

t is about 1 to about 6.