Surfactant-compatible star macromolecules

• US 10,336,848 B2
• Filed: 07/02/2015
• Issued: 07/02/2019
• Est. Priority Date: 07/03/2014
• Status: Active Grant

• Current Assignee: Pilot Polymer Technologies Incorporated
• Original Assignee: Pilot Polymer Technologies Incorporated
• Inventors: Huang, Liang, Liao, Yuanxi, McCarthy, Patrick
• Primary Examiner(s): Chin, Hui H
• Application Number:
  US15/322,967
• Publication Number:
  US 20180072832A1
• Time in Patent Office: 1,461 Days
• Field of Search: 524 58
• CPC Class Codes: C08F 20/18 with acrylic or methacrylic acids
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: C08L 2201/54 Aqueous solutions or dispersions
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Abstract

The present invention relates to multi-arm surfactant-system thickening star macromolecules, and methods of preparing and using the same. In one aspect of the invention, a surfactant-system thickening star macromolecule is capable of providing surfactant-compatibility, increase the viscosity of a surfactant-containing system, and/or temperature-stability to an aqueous composition.

Claims

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

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

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.

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.

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.

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

[L¹—

G¹—

L²—

G²];

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.

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:

[L¹—

G¹—

L²—

G²]

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 at least one second polymeric arm; and

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

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:

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