Poly(alkyenylamide)-polysaccharide hydrogels for treatment of subterranean formations

Patent metadata

Field	Value
Publication number	US-9587469-B2
Application number	US-201313948620-A
Country	US
Kind code	B2
Filing date	Jul 23, 2013
Priority date	Jul 23, 2013
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The present invention provides compositions including poly(alkenylamide)-polysaccharide hydrogels for treating a subterranean formation and methods of using the same. In various embodiments, the present invention provides a method of treating a subterranean formation, including obtaining or providing a composition including a poly(alkenylamide)-polysaccharide hydrogel. The method also includes placing the composition in a subterranean formation. In some embodiments, the poly(alkenylamide)-polysaccharide hydrogel is a polyacrylamide-alginate hydrogel.

First claim

What is claimed is:

1. A method of treating a subterranean formation, the method comprising:
placing in the subterranean formation a composition comprising a poly(alkenylamide)-polysaccharide hydrogel; and
plugging a flow pathway in the subterranean formation with the hydrogel;
wherein
the poly(alkenylamide) comprises the structure -(PAA) n -(CL) m -,
the poly(alkenylamide) is a block or random copolymer,
PAA has the structure

CL has the structure:

the poly(alkenylamide)-polysaccharide hydrogel comprises at least one crosslink comprising an imide between the poly(alkenylamide) and the polysaccharide,
each of PAA and CL at each occurrence independently occur in the orientation shown or in the opposite orientation,
the polysaccharide comprises Structure I

each of R 10 , R 11 , R 12 , R 13 , and R 14 are independently selected from the group consisting of —H, —R 15 , —OR 15 , and —C(O)R 16 ,
at each occurrence R 15 is independently selected from the group consisting of —H and C 1 -C 10 hydrocarbyl,
at each occurrence R 16 is independently selected from the group consisting of —O − , —OH, and —O − CI + ,
at each occurrence CI + is independently a counterion,
p is at least about 2,
each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 at each occurrence is independently selected from the group consisting of —H and C 1 -C 10 hydrocarbyl,
each of L 1 , L 2 , and L 3 are independently at each occurrence selected from the group consisting of a bond and C 1 -C 10 hydrocarbylene,
m is at least about 1,
n is at least about 2, and
m1 is about 0 to about 10,000,000.

2. The method of claim 1 , wherein the polysaccharide has the structure

wherein E is independently at each occurrence selected from the group consisting of H, —R′, —OH, and —OR′ wherein R′ at each occurrence is independently substituted or unsubstituted C 1 -C 10 hydrocarbyl, and wherein p is about 2 to about 100,000,000.

3. The method of claim 1 , wherein Structure I is

4. The method of claim 1 , wherein Structure I is

wherein each of R 11 , R 12 , R 13 , and R 14 are independently selected from the group consisting of —H, and —OH, wherein R 10 at each occurrence is independently —C(O)R 16 , wherein at each occurrence R 16 is independently selected from the group consisting of —O − , —OH, and —O − CI + , wherein p is about 10 to about 100,000.

5. The method of claim 4 , wherein at each occurrence CI + is independently selected from the group consisting of Na + , K + , Li + , H + , Zn + , NH 4 + , Ca 2+ , Mg 2+ , Zn 2+ and Al 3+ .

6. The method of claim 4 , wherein CI + is Ca 2+ .

7. The method of claim 1 , wherein Structure I is

wherein q1 is about 1 to about 100,000,000, q2 is about 1 to about 100,000,000, and q1+q2=p.

8. The method of claim 1 , wherein R 10 is —C(O)R 16 , wherein at each occurrence R 16 is independently selected from the group consisting of —O, —OH, and —O − CI + , wherein at each occurrence CI + is independently a counterion; R 11 and R 14 are —H; and R 12 and R 13 are —OH.

9. A The method of claim 1 , wherein Structure I is

wherein at each occurrence R 16 is independently selected from the group consisting of —O − , —OH, and —O − CI + , wherein at each occurrence CI + is independently a counterion, q1 is about 1 to about 100,000,000, q2 is about 1 to about 100,000,000, and q1+q2=p.

10. The method of claim 1 , wherein the polysaccharide has a molecular weight of about 500 g/mol to about 100,000.000 g/mol.

11. The method of claim 1 , wherein the polysaccharide has a molecular weight of about 1,000 g/mol to about 5,000,000 g/mol.

12. The method of claim 1 , wherein the imide is formed by reaction between an amide group of the poly(alkenylamide) and a carboxylic acid or salt thereof of the polysaccharide.

13. The method of claim 1 , wherein the polysaccharide is alginic acid or a salt thereof.

14. The method of claim 1 , wherein the poly(alkenylamide)-polysaccharide hydrogel comprises the following structure -(PAA) n1 -(CL) n2 -(PAA-PS) n3 -, wherein PAA, CL, PAA-PS, and the repeating units of PAA, CL, and PAA-PS are in a block copolymer or random copolymer arrangement; wherein PAA has the structure

wherein CL has the structure

wherein at each occurrence PAA-PS is part of the same polysaccharide or a different polysaccharide, wherein PAA-PS has the structure

wherein
at each occurrence each of PAA, CL, and PAA-PS independently occurs in the orientation shown or in the opposite orientation;
each of R 1 , R 2 , R 3 , R 4 , and R 5 at each occurrence is independently selected from the group consisting of —H and C 1 -C 10 hydrocarbyl;
each of L 1 , L 2 , and L 3 at each occurrence is selected from the group consisting of a bond and C 1 -C 10 hydrocarbylene;
each of R 10 , R 11 , R 12 , R 13 , and R 14 are independently selected from the group consisting of —H, —R 15 , —OR 15 , and —C(O)R 16 , wherein at each occurrence R 15 is independently selected from the group consisting of —H and C 1 -C 10 hydrocarbyl, and wherein at each occurrence R 16 is independently selected from the group consisting of —O − , —OH, and —O − CI + , wherein at each occurrence CI + is independently a counterion;
n1 is about 0 to about 100,000,000, n3 is about 1 to about 100,000,000, and n1+n3 is at least about 2;
n2 is about 0 to about 100,000,000; and

p1 is about 1 to about 100,000,000, p2 is about 1 to about 100,000,000, and p1+p2 is at least about 2.

15. The method of claim 14 , wherein
each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is —H;
R 10 is —C(O)R 16 , and at each occurrence R 16 is independently selected from the group consisting of —O − , —OH, and —O − CI + ;
L 1 and L 2 is a bond;
L 3 is methylene;
n1 is about 0 to about 100,000, n3 is about 1 to about 100,000, and n1+n3 is about 10 to about 100,000;
n2 is about 0 to about 10,000; and
p1 is about 1 to about 100,000, p2 is about 1 to about 100,000, and p1+p2 is about 10 to about 100,000.

16. The method of claim 14 , wherein PAA has the structure

wherein CL has the structure

wherein

Assignees

• Halliburton Energy Services Inc

Inventors

• Miller Matthew Lynn

Classifications

• C09K8/514

  of natural origin, e.g. polysaccharides, cellulose (C09K8/512 takes precedence) · CPC title

• C09K8/887

  containing cross-linking agents · CPC title

• C09K8/90

  of natural origin, e.g. polysaccharides, cellulose · CPC title

• C09K8/68

  containing organic compounds · CPC title

• C09K8/70

  characterised by their form or by the form of their components, e.g. foams · CPC title