Salt-Tolerant Star Macromolecules

• US 20170355803A1
• Filed: 01/25/2017
• Published: 12/14/2017
• Est. Priority Date: 02/04/2013
• Status: Active Grant

• Current Assignee: Pilot Polymer Technologies Incorporated
• Original Assignee: ATRP Solutions, Inc. (Pilot Chemical Corp.)
• Inventors: Huang, Liang, Liao, Yuanxi, McCarthy, Patrick
• Granted Patent: US 10,259,901 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• 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: C08F 8/12 Hydrolysis
• CPC Class Codes: C08J 2300/206 Star polymers
• CPC Class Codes: C09K 8/035 Organic additives

Abstract

The present invention relates to multi-arm salt-tolerant star macromolecules, and methods of preparing and using the same. In one aspect of the invention, a salt-tolerant star macromolecule is capable of providing salt-tolerance to an aqueous composition.

Claims

1. A salt-tolerant star macromolecule that when dissolved in water at a concentration of at least 0.3 wt. % forms a homogeneous gel and has a dynamic viscosity of at least 10,000 cP in a 0.4 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.

2. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule has a dynamic viscosity in a NaCl-containing aqueous solution that is greater than the dynamic viscosity at 0.0 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.

3. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule has an increase in dynamic viscosity with an increase in NaCl concentration, according to the Salt Tolerance Test.

4. The salt-tolerant star macromolecule of claim 1, wherein the dynamic viscosity of the salt-tolerant star macromolecule in a 0.2 wt % NaCl aqueous solution is at least 40% of the dynamic viscosity at 0.0 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.

5. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule comprises:

i) a core;

ii) a plurality of hydrophilic polymeric arms; and

iii) at least one salt-tolerant-enhancing copolymeric arm, comprising;

a) a hydrophilic polymeric segment proximal to the core; and

b) a salt-tolerant-enhancing polymeric segment distal to the core.

6. The salt-tolerant star macromolecule of claim 5, wherein the salt-tolerant-enhancing polymeric segment comprises:

i) repeat units of monomeric residues of one or more polymerized salt-tolerant-enhancing monomers; and

ii) optionally, repeat units of monomeric residues of one or more polymerized hydrophobic or hydrophilic monomers.

7. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule is represented by Formula Z:

8. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule has a molecular weight (Mn) in the range of from 5,000 g/mol to 10,000,000 g/mol.

9. The salt-tolerant star macromolecule of claim 1, wherein the arms of the salt-tolerant star macromolecule independently have a molecular weight (Mn) in the range of from 1,000 g/mol to 250,000 g/mol.

10. The salt-tolerant star macromolecule of claim 1, wherein the monomeric residues of one or more polymerized hydrophobic and hydrophilic monomers are present in the salt-tolerant-enhancing polymeric segment P2.

11. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule comprises a mixture of 2 or more arm types.

12. The salt-tolerant star macromolecule of claim 1, wherein the salt-tolerant star macromolecule comprises a mixture of 3 or more arm types.

13. The salt-tolerant star macromolecule of claim 1, wherein the dynamic viscosity of the salt-tolerant star macromolecule at 80°

C. is at least 50% relative to viscosity of the gel at 25°

C., according to the Temperature Stability Test.

14. The salt-tolerant star macromolecule of claim 1, wherein the dynamic viscosity of the salt-tolerant star macromolecule at 60°

C. is at least 60% relative to viscosity of the gel at 25°

C., according to the Temperature Stability Test.

15. A salt-tolerant thickening agent, comprising the salt-tolerant star macromolecule of claim 1.

16. A method of making a salt-tolerant composition, comprising:

adding the salt-tolerant star macromolecule of claim 1, that when dissolved in water at a concentration of at least 0.3 wt. % forms a homogeneous gel and has a dynamic viscosity of at least 10,000 cP in a 0.4 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.

17. A method of making an aqueous composition salt-tolerant, comprising:

adding at least 0.3 wt. % of the salt-tolerant star macromolecule of claim 1 to the aqueous composition;

wherein the salt-tolerant star macromolecule when dissolved in water at a concentration of at least 0.3 wt. % forms a homogeneous gel and has a dynamic viscosity of at least 10,000 cP in a 0.4 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.

18. A one-pot method of preparing a star macromolecule, comprising:

i) preparing one or more of a first arm, comprising;

a) feeding a first amount of a radical initiator in a controlled manner to a reaction vessel containing a first group of monomers at a pre-determined temperature; and

b) polymerizing the first group of monomers to greater than 15% monomer conversion;

ii) preparing one or more of a second arm and, optionally, extending the prepared one or more first arms, comprising;

a) adding a second arm initiator to the reaction vessel;

b) adding a second group of monomers to the reaction vessel;

c) feeding a second amount of the radical initiator in a controlled manner to the reaction vessel containing the second arm initiator, the second group of monomers, and optionally the prepared one or more first arms, at a pre-determined temperature; and

d) polymerizing the second group of monomers to greater than 70% monomer conversion;

iii) optionally, repeating step ii) to prepare one or more of a third arm;

iv) crosslinking the prepared one or more first arms, the prepared one or more second arms, and optionally, the prepared one or more third arms; and

v) isolating the prepared star macromolecule.

19. The one-pot method of claim 18, wherein the one-pot method reduces the preparation time by at least 75%, relative to multi-pot preparations.

20. The one-pot method of claim 18, wherein the prepared star macromolecule comprises a salt-tolerant star macromolecule that when dissolved in water at a concentration of at least 0.3 wt. % forms a homogeneous gel and has a dynamic viscosity of at least 10,000 cP in a 0.4 wt. % NaCl aqueous solution, according to the Salt Tolerance Test.