Pendant epoxide polymers and methods of treating subterranean formations

Patent metadata

Field	Value
Publication number	US-10005930-B2
Application number	US-201615263661-A
Country	US
Kind code	B2
Filing date	Sep 13, 2016
Priority date	Sep 14, 2015
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

This document relates to compositions including a crosslinkable polymer including a pendant epoxide repeat unit and an amine crosslinker, and methods of treating a subterranean formation by providing the composition to the formation. The pendant epoxide repeat unit has the structure

Each R 1 is independently a (C 1 -C 10 ) alkylene or (C 1 -C 10 ) alkylene ether, each alkylene ether independently having a ratio of carbon atoms to oxygen atoms of 1:1 to 4:1.

First claim

What is claimed is:

1. A liquid composition comprising:
a crosslinkable polymer comprising a pendant epoxide repeat unit,
wherein the pendant epoxide repeat unit has the structure:

wherein each R1 is independently a (C1-C10) alkylene or (C1-C10) alkylene ether, each alkylene ether independently having a ratio of carbon atoms to oxygen atoms of 1:1 to 4:1;
a liquid solvent; and
an amine crosslinker, wherein the liquid solvent is a hydrocarbon fluid selected from the group consisting of kerosene, xylenes, toluene, diesel, mineral oils, napthenic oils, synthetic oils and paraffins.

2. The composition of claim 1 , wherein the pendant epoxide repeat unit is about 1% to about 30% by weight of the crosslinkable polymer.

3. The composition of claim 1 , wherein the crosslinkable polymer further comprises a hydrocarbylene repeat unit, wherein the hydrocarbylene repeat unit is a substituted or unsubstituted (C2-C15) hydrocarbylene.

4. The composition of claim 3 , wherein the hydrocarbylene repeat unit is about 50% to about 99% by weight of the crosslinkable polymer.

5. The composition of claim 1 , wherein the crosslinkable polymer further comprises an ester repeat unit having the structure

wherein
each L is independently a substituted or unsubstituted (C1-C10) hydrocarbylene;
each R2 is independently a bond or a substituted or unsubstituted (C1-C20) hydrocarbylene; and
each R3 is independently —H or a substituted or unsubstituted (C1-C10) hydrocarbyl.

6. The composition of claim 5 , wherein the ester repeat unit is about 10% to about 40% by weight of the crosslinkable polymer.

7. The composition of claim 1 , wherein the crosslinkable polymer comprises:
a pendant epoxide repeat unit having the structure:

wherein each R1 is —CH2;
a hydrocarbylene repeat unit having the structure:

 and
an ester repeat unit having the structure:

8. The composition of claim 1 , wherein the crosslinkable polymer has a melt index of about 4 g/10 min to about 8 g/10 min.

9. The composition of claim 1 , wherein the crosslinkable polymer has a melting point of about 50° C. to about 80° C.

10. The composition of claim 1 , wherein the crosslinkable polymer has a Vicat softening point of less than about 60° C.

11. The composition of claim 1 , wherein the crosslinkable polymer has a tensile strength of about 3 MPa to about 5 MPa.

12. The composition of claim 1 , wherein the crosslinkable polymer has a Shore D hardness of about 10 to about 25.

13. The composition of claim 1 , wherein the amine crosslinker comprises at least one of a polyalkyleneimine, a polyetheramine, a polyalkylenepolyamine, an aliphatic amine, a polyfunctional aliphatic amine, an arylalkylamine, a heteroarylalkylamine, a chitosan, and combinations thereof.

14. The composition of claim 13 , wherein the amine crosslinker comprises at least one of a polyethyleneimine, an ethylenediamine, a diethylenetriamine (DETA), a triethylenetetramine (TETA), a tetraethylenepentamine (TEPA), a 1,2-propylenediamine, a 1,3-propylenediamine, a dipropylenetriamine, a tripropylenetetramine, a tetrapropylenepentamine, an ethylene propylene triamine, an ethylene dipropylene tetramine, a diethylene propylene pentamine, an ethylene tripropylene pentamine, a diethylene dipropylene pentamine, a triethylene propylene pentamine, a polyethylenimine, a poly(ethyleneoxy)amine, a poly(propyleneoxy)amine, and combinations thereof.

15. The composition of claim 1 , wherein the weight ratio of the crosslinkable polymer to the amine crosslinker is about 10:1 to about 1:2.

16. The composition of claim 1 , wherein the composition further comprises a carrier solvent.

17. The composition of claim 1 , wherein the crosslinkable polymer and amine crosslinker are about 1% to about 30% by weight of the composition.

18. The composition of claim 1 , wherein the composition has a gel time of less than about 120 hours at about 80° C.

19. A method of treating a subterranean formation comprising:
providing in a subterranean formation a liquid composition comprising
a crosslinkable polymer comprising a pendant epoxide repeat unit, wherein the pendant epoxide repeat unit has the structure:

wherein each R1 is independently a (C1-C10) alkylene or (C1-C10) alkylene ether, each alkylene ether independently having a ratio of carbon atoms to oxygen atoms of 1:1 to 4:1;
a liquid solvent; and
an amine crosslinker; and

crosslinking the composition to form a sealant gel, wherein the liquid solvent is a hydrocarbon fluid selected from the group consisting of kerosene, xylenes, toluene, diesel, mineral oils, napthenic oils, synthetic oils and paraffins.

20. The method of claim 19 , wherein crosslinking the composition to form the sealant gel occurs near a casing, a casing-casing annulus, a tubing-casing annulus, or in a void in at least one of a cement sheath and a pipe, and crosslinking the composition to form the sealant gel prevents or retards undesired loss or leak off of fluid into the formation.

Assignees

• Saudi Arabian Oil Co

Inventors

• Reddy B Raghava

Classifications

• C09K8/035

  Organic additives · CPC title

• C09K8/428

  for squeeze cementing, e.g. for repairing · CPC title

• C08G59/3209

  obtained by polymerisation of unsaturated mono-epoxy compounds · CPC title

• C08G59/502

  Polyalkylene polyamines · CPC title

• C08G59/504

  containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen · CPC title