IP Library Granted Patent US 10,179,855
Granted Patent B2
US 10,179,855 · App. 15/190,364 · Granted Jan 15, 2019

Methods of making acrylamide-acrylic acid copolymers

Inventors: Stephen Marrou (Oak Park, IL); Xiangyang Zhu (Denver, CO); Heqing Huang (Naperville, IL)
Assignee: Ecolab USA Inc.
C08L71/02C08F220/56
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Quick Facts
Patent No.
US 10,179,855
App. No.
15/190,364
Granted
Jan 15, 2019
Kind
B2
Abstract

A method of making acrylamide-acrylic acid copolymers in water-in-oil latices is described. The method results in a copolymer having randomly distributed carboxylate functionalities and is suitable for ionic crosslinking. The copolymers and their ionically crosslinked counterparts are useful for enhanced oil recovery processes.

Claims (32)

1. A composition comprising a water-in-oil latex, the water-in-oil latex comprising a water phase and an oil phase, the water phase comprising water, acrylamide, and acrylic acid and having a pH of about 3.0 to 4.5; wherein the latex further comprises a surfactant mixture consisting essentially of nonionic surfactants and comprising a block copolymer.

2. The composition of claim 1 wherein the water phase consists essentially of water, acrylamide, and acrylic acid, wherein the pH of the water phase is about 3.0 to 4.5.

3. The composition of claim 1 wherein the ratio of acrylamide to acrylic acid is about 60:40 to 99:1.

4. The composition of claim 1 wherein the block copolymer is a triblock copolymer comprising at least one block consisting essentially of ethylene glycol repeat units and having an HLB of about 4 to 6.

5. The composition of claim 4 wherein the triblock copolymer further comprises at least one block consisting essentially of hydroxyacid repeat units.

6. The composition of claim 5 wherein the hydroxyacid is 12-hydroxystearic acid.

7. The composition of claim 1 wherein the pH is about 3.5 to 4.0.

8. A composition comprising a water-in-oil latex formed by a method comprising

a. combining water and monomers to form a water phase, the monomers comprising acrylamide and acrylic acid;

b. adjusting the pH of the water phase to between about 3.0 to 4.5;

c. combining a hydrocarbon solvent with a surfactant mixture to form an oil phase, the surfactant mixture consisting essentially of nonionic surfactants and comprising a block copolymer;

d. contacting the water phase and the oil phase to form a water-in-oil latex;

e. polymerizing the monomers to form a copolymer; and

f. neutralizing the water phase.

9. The composition of claim 8 further comprising the product of diluting the composition with a water source after neutralizing, wherein the copolymer concentration after diluting is about 0.01 wt % to 1.00 wt %.

10. The composition of claim 9 wherein the water source comprises water and a salt of Ca 2+ , Fe +2 , Fe +3 , Mg 2+ , Cr 2+ , Cr 3+ , Zn 2+ , or Al 3+ .

11. The composition of claim 10 wherein the salt is aluminum citrate or chromium acetate.

12. The composition of claim 8 wherein the ratio of acrylamide to acrylic acid units in the copolymer is about 50:50 to 99:1.

13. The composition of claim 8 wherein the neutralizing comprises contacting the composition with sodium hydroxide and an alkanolamide surfactant.

14. The composition of claim 13 wherein the alkanolamide surfactant is N,N-diethanololeamide.

15. A method of making a water-in-oil copolymer latex, the method comprising

a. combining water and monomers to form a water phase, the monomers comprising acrylamide and acrylic acid;

b. adjusting the pH of the water phase to between about 3.0 to 4.5;

c. combining a hydrocarbon solvent with a surfactant mixture to form an oil phase, the surfactant mixture consisting essentially of nonionic surfactants and comprising a block copolymer;

d. contacting the water phase and the oil phase to form a water-in-oil latex;

e. polymerizing the monomers to form a copolymer; and

f. neutralizing the water phase.

16. The method of claim 15 further comprising diluting the latex with a water source after neutralizing, wherein the copolymer concentration after diluting is about 0.01 wt % to 1.00 wt %.

17. The method of claim 16 wherein the water source comprises water and a salt of Ca 2+ , Mg 2+ , Cr 2+ , Cr 3+ , Zn 2+ , or Al 3+ .

18. The method of claim 17 wherein the salt is aluminum citrate or chromium acetate.

19. The method of claim 15 wherein the neutralizing comprises contacting the composition with a neutralizing solution, the neutralizing solution comprising sodium hydroxide and an alkanolamide surfactant.

20. A method of diluting a water-in-oil copolymer latex, the method comprising adding a water source to the water-in-oil copolymer latex of claim 15 after the neutralizing, wherein the water source comprises water and a salt of Ca 2+ , Mg 2+ , Cr 2+ , Cr 3+ , Zn 2+ , or Al 3+ ; and the copolymer concentration after diluting is about 0.01 wt % to 1.00 wt %.

Assignments (9)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 17, 2025
From: JPMORGAN CHASE BANK, N.A.
To: CHAMPIONX LLC; APERGY ESP SYSTEMS, LLC; APERGY BMCS ACQUISITION CORP; HARBISON-FISCHER, INC.; NORRIS RODS, INC.,; NORRIS RODS, INC.,; NORRISEAL-WELLMARK, INC.; PCS FERGUSON, INC.; QUARTZDYNE, INC.; US SYNTHETIC CORPORATION
Reel/Frame 072004/0019 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 19, 2024
From: CHAMPIONX USA INC.
To: CHAMPIONX LLC
Reel/Frame 067768/0888 →
SECURITY INTEREST Recorded Jun 8, 2022
From: APERGY BMCS ACQUISITION CORP.; APERGY ESP SYSTEMS, LLC; CHAMPIONX USA INC.; HARBISON-FISCHER, INC.; NORRIS-RODS, INC.; PCS FERGUSON, INC.; THETA OILFIELD SERVICES, INC.; US SYNTHETIC CORPORATION
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 060313/0456 →
RELEASE OF SECURITY INTEREST Recorded Jun 7, 2022
From: BANK OF AMERICA, N.A.
To: CHAMPIONX USA INC.
Reel/Frame 060304/0267 →
RELEASE OF SECURITY INTEREST Recorded Jun 7, 2022
From: BANK OF AMERICA, N.A.
To: CHAMPIONX USA INC.
Reel/Frame 060304/0403 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 10, 2020
From: ECOLAB USA INC.
To: CHAMPIONX USA INC.
Reel/Frame 053749/0001 →
SECURITY INTEREST Recorded Jun 5, 2020
From: CHAMPIONX USA INC.
To: BANK OF AMERICA, N.A.
Reel/Frame 052848/0810 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 1, 2019
From: MARROU, STEPHEN; ZHU, XIANGYANG; HUANG, HEQING
To: ECOLAB USA INC.
Reel/Frame 048219/0598 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 23, 2016
From: MARROU, STEPHEN; ZHU, XIANGYANG; HUANG, HEQING
To: ECOLAB USA INC.
Reel/Frame 038993/0816 →
Continuity (2)
Provisional Application 62186100 · Jun 29, 2015
Related Publication 20160376390A1 · Dec 29, 2016