Associative copolymers with hydrophobic quaternized (meth)acrylamide and (meth)acrylic acid derivatives

Patent metadata

Field	Value
Publication number	US-11649396-B2
Application number	US-201916972823-A
Country	US
Kind code	B2
Filing date	Jun 3, 2019
Priority date	Jun 6, 2018
Publication date	May 16, 2023
Grant date	May 16, 2023

Abstract

The present invention relates to a process for the preparation of a water-soluble copolymer comprising the step of reacting a monomer (a) of formula (I), wherein Q 1 , Q 2 , R 1 to R 7 and X have the meaning as indicated in the description and claims with at least one monoethylenically unsaturated, anionic monomer (b), preferably representing a monoethylenically unsaturated monomer comprising at least one carboxy, phosphonate or sulfonate group and salts thereof, preferably their ammonium salts or alkaline-earth metal salts or alkali metal salts; and at least one monoethylenically unsaturated, non-ionic monomer (c). The present invention further relates to a copolymer obtainable by said process and its use in enhanced oil recovery (EOR), a formulation comprising said copolymer and a method of oil production uses said formulation.

First claim

The invention claimed is:

1. A process for the preparation of a water-soluble copolymer comprising the step of
reacting a monomer (a) of formula (I)

wherein
Q 1 is O or NH;
R 1 and R 2 are H;
R 3 is H or CH 3 ;
R 5 , R 6 are independently selected from the group consisting of CH 3 and C 2 H 5 ;
Q 2 is an alkylene chain having 2 to 8 carbon atoms;
R 7 is a hydrocarbon radical having 10 to 14 carbon atoms;
X is a counter ion having a negative charge;
with at least one monoethylenically unsaturated, anionic monomer (b) selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropane sulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid and their salts thereof, and ammonium; and
at least one monoethylenically unsaturated, non-ionic monomer (c) selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone;
wherein the reaction is carried out in the presence of at least a first additive, wherein the at least first additive has the formula R 10 —(OQ 3 ) n -OH, wherein R 10 is a hydrocarbon radical having 8 to 30 carbon atoms, each Q 3 is independently an alkylene group having 2 to 6 carbon atoms, and n is a number from 8 to 20.

2. The process of claim 1 , wherein Q 1 is O;
with at least one monoethylenically unsaturated, anionic monomer (b) selected from the group consisting of water-soluble salts of an alkali metal, alkaline-earth metal and ammonium; and at least one monoethylenically unsaturated, non-ionic monomer (c) selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone; wherein the reaction is carried out in the presence of at least a first additive, wherein the at least first additive has the formula R 10 —(OQ 3 ) n -OH, wherein R 10 is a hydrocarbon radical having 8 to 30 carbon atoms, each Q 3 is ethylene, and n is a number from 8 to 20.

3. The process of claim 1 , wherein the copolymer has a molecular weight greater than 500,000 g/mol.

4. The process of claim 1 , wherein the copolymer comprises monomers (a), (b) and (c) in an amount of at least 90 mol-% based on the total amount of all monomers of the copolymer.

5. The process of claim 1 , wherein at least one of the following requirements is fulfilled:
Q 2 is an alkylene chain having 2 to 6 carbon atoms;
X is halide.

6. The process of claim 1 , wherein monomer (a) is a monomer of formula (I) wherein
Q 1 is NH, R 1 and R 2 are H, R 3 is CH 3 , R 5 and R 6 are CH 3 R 7 is an unbranched alkyl chain having 12 carbon atoms;
Q 1 is NH, R 1 and R 2 are H, R 3 is H, R 5 and R 6 are CH 3 R 7 is an unbranched alkyl chain having 12 carbon atoms;
Q 1 is O, R 1 and R 2 are H, R 3 is CH 3 , R 5 and R 6 are CH 3 R 7 is an unbranched alkyl chain having 12 carbon atoms; or
Q 1 is O, R 1 and R 2 are H, R 3 is H, R 5 and R 6 are CH 3 R 7 is an unbranched alkyl chain having 12 carbon atoms.

7. The process of claim 1 , wherein the at least one monoethylenically unsaturated, anionic monomer (b) is acrylic acid, methacrylic acid, 2-acryl-2-methylpropane sulfonic acid, or a salt thereof.

8. The process of claim 1 , wherein the least one monoethylenically unsaturated, non-ionic monomer (c) is water-soluble.

9. The process of claim 1 , wherein the least one monoethylenically unsaturated, non-ionic monomer (c) is water-soluble, acrylamide or methacrylamide.

10. The process of claim 1 , wherein the reaction is carried out with
0.01 mol-% to 1 mol-% monomer (a),
9 mol-% to 70 mol-% monomer (b),
29 mol-% to 90.99 mol-% monomer (c),
each based on the total amount of all monomers of the copolymer.

11. The process of claim 1 , wherein the reaction is carried out with
0.05% to 0.5% monomer (a),
15% to 40% monomer (b),
59.5% to 84.5% monomer (c),
each based on the total amount of all monomers of the copolymer.

12. The process of claim 1 , wherein the reaction is carried out in the presence of at least the first additive and a second additive, wherein the second additive is a sulfosuccinate of formula (II)

wherein
R 8 , R 9 are independently a hydrocarbon radical having 4 to 32 carbon atoms; and
Y is a counter ion with a positive charge.

13. The process of claim 12 , wherein R 8 and R 9 are the same and are a hydrocarbon radical having 4 to 20 carbon atoms; and Y is an alkali cation.

14. The process of claim 12 , wherein the second additive is sodium diisooctyl sulfosuccinate.

15. The process of claim 1 , wherein the molar ratio of first additive, the second additive or the first and the second additive to monomer (a) is 1:10 to 10:1.

16. The process of claim 1 , wherein the process is a free-radical polymerization undertaken by means of gel polymerization, in an adiabatic gel polymerization in aqueous phase.

17. A water-soluble copolymer obtainable by the process of claim 1 .

18. An aqueous formulation comprising water and at least one copolymer of claim 17 .

19. A process for mineral oil production, comprising the steps of injecting an aqueous formulation of claim 18 into a mineral oil deposit through an injection well and withdrawing crude oil from the deposit through at least one production well.

Assignees

• Basf Se

Inventors

• Langlotz Bjoern
• Bittner Christian
• Stein Stefan

Classifications

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C09K8/588 Primary

  characterised by the use of specific polymers {(polymeric surfactants C09K8/584)} · CPC title

• C09K8/035

  Organic additives · CPC title

• C08F220/56

  Acrylamide; Methacrylamide · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title