Degradable extrusion resistant compositions and articles of manufacture

1. A degradable polymer composition comprising:

a polyurethane comprising ester groups in a backbone of the polyurethane and carboxylic acid groups attached to the backbone of the polyurethane; and

a filler comprising a powder comprising particles having an average size of about 5 microns to about 500 microns or a combination of the powder and a fiber having an average length of about ⅛ inch to about 5 inches,

wherein the powder comprises one or more of the following: sodium chloride; a dissolvable silicate; aluminum hydroxide oxide; adipic acid; or succinic acid, the dissolvable silicate comprising about 66 to about 80 wt. % of SiO 2 , about 0 to about 35 of Na 2 O, 0 to about 35 wt. % of K 2 O, 0 to about 20 wt. % of CaO, and 0 to about 10 wt. % of MgO, provided that the sum of the weights of Na 2 O and K 2 O is about 20 wt. % to about 40 wt. %, each based on the total weight of the dissolvable silicate.

2. The composition of claim 1 , wherein the carboxylic acid groups are present in an amount of about 1 wt. % to about 15 wt. % based on the total weight of the polyurethane.

3. The composition of claim 1 , wherein the polyurethane is derived from a polyisocyanate, a polyol, and a carboxylic acid functionalized alcohol, and wherein at least one of the polyisocyanate and the polyol comprise polyester groups.

4. The composition of claim 3 , wherein the carboxylic acid functionalized alcohol comprises at least two hydroxyl groups.

5. The composition of claim 4 , wherein the carboxylic acid functionalized alcohol comprises 2,2-bis(hydroxymethyl)propionic acid.

6. The composition of claim 1 , wherein the polyurethane is derived from a polyurethane prepolymer, a curative, and a carboxylic acid functionalized alcohol, the polyurethane prepolymer comprising ester groups.

7. The composition of claim 1 , wherein the polyurethane is derived from a curative, a crosslinking agent, a carboxylic acid functionalized alcohol, and a prepolymer comprising one or more of the following: a diisocyanate-terminated polyester prepolymer; or an isocyanate-terminated diphenylmethane diisocyanate polyester prepolymer.

8. The composition of claim 1 , wherein the filler comprises a combination of the fiber and the powder, and the fiber comprises one or more of the following: carbon fiber; glass fiber; or polymer fiber.

9. The composition of claim 1 , wherein the filler comprises the powder and the fiber.

10. The degradable polymer composition of claim 9 , wherein the weight ratio of the powder relative to the fiber is about 10:1 to about 1:1.

11. The composition of claim 1 , wherein the weight ratio of the polyurethane to the filler is about 50:1 to about 1:1.

12. The composition of claim 1 , wherein the composition disintegrates into a liquid at a temperature equal to or lower than about 200° F. in a fluid comprising water or brine.

13. An article comprising the composition of claim 1 .

14. The article of claim 13 , wherein the article is a pumpable tool comprising a plug, a direct connect plug, a bridge plug, a wiper plug, a frac plug, a component of a frac plug, a drill in sand control beaded screen plug, an inflow control device plug, a polymeric plug, a disappearing wiper plug, a cementing plug, a ball, a diverter ball, a shifting and setting ball, a swabbing element protector, a buoyant recorder, a pumpable collet, a float shoe, or a dart.

15. The article of claim 13 , wherein the article is a tool that inhibits flow comprising a seal, a high pressure beaded frac screen plug, a screen basepipe plug, a coating for a balls and a seat, a compression packing element, an expandable packing element, an O-ring, a attached seal, a bullet seal, a sub-surface safety valve seal, a sub-surface safety valve flapper seal, a dynamic seal, a V-ring, a backup ring, a drill bit seal, a liner port plug, an atmospheric disc, an atmospheric chamber disc, a debris barrier, a drill in stim liner plug, an inflow control device plug, a flapper, a seat, a ball seat, a direct connect disk, a drill-in linear disk, a gas lift valve plug, a fluid loss control flapper, an electric submersible pump seal, a shear out plug, a flapper valve, a gaslift valve, or a sleeve.

16. The degradable polymer composition of claim 1 , wherein the powder comprises the dissolvable silicate, and the dissolvable silicate comprises sodium silicate having a formula of Na 2 O.SiO 2 , wherein the weight percent of SiO 2 relative to Na 2 O is about 3.22:1 to about 1:1.

17. A method of manufacturing a degradable article, the method comprising:

compressing a combination of a filler and a polyurethane forming composition at a temperature of about 20° C. to about 150° C. and a pressure of about 100 psi to about 10,000 to provide a molded part, the filler comprising a powder comprising particles having an average size of about 5 microns to about 500 microns or a combination of the powder and a fiber having an average length of about ⅛ inch to about 5 inches; and

heating the molded part at a temperature of about 60° C. to about 150° C. to provide the disintegrable article;

wherein the polyurethane forming composition comprises a first composition comprising a polyol component, a polyisocyanate component, and a first carboxylic acid functionalized alcohol; or a second composition comprising a polyurethane prepolymer, a curative, and a second carboxylic acid functionalized alcohol; or a combination of the first composition and the second composition,

wherein the powder comprises one or more of the following: sodium chloride; a dissolvable silicate; aluminum hydroxide oxide; adipic acid; or succinic acid, the dissolvable silicate comprising about 66 to about 80 wt. % of SiO 2 , about 0 to about 35 of Na 2 O, 0 to about 35 wt. % of K 2 O, 0 to about 20 wt. % of CaO, and 0 to about 10 wt. % of MgO, provided that the sum of the weights of Na 2 O and K 2 O is about 20 wt. % to about 40 wt. %, each based on the total weight of the dissolvable silicate.

18. A method to degrade an article, the method comprising:

exposing the article to a fluid at a temperature of about 25° C. to about 300° C.,

the article comprising a polyurethane that comprises ester groups in a backbone of the polyurethane and carboxylic acid groups attached to the backbone of the polyurethane; and a filler comprising one or more of the following: a powder comprising particles having an average particle size of about 5 microns to about 500 microns; or a combination of the powder with a fiber having an average length of about ⅛ inch to about 5 inches,

wherein the powder comprises one or more of the following: sodium chloride; a dissolvable silicate; aluminum hydroxide oxide; adipic acid; or succinic acid, the dissolvable silicate comprising about 66 to about 80 wt. % of SiO 2 , about 0 to about 35 of Na 2 O, 0 to about 35 wt. % of K 2 O, 0 to about 20 wt. % of CaO, and 0 to about 10 wt. % of MgO, provided that the sum of the weights of Na 2 O and K 2 O is about 20 wt. % to about 40 wt. %, each based on the total weight of the dissolvable silicate.

19. The method of claim 18 , wherein the article is exposed to the fluid at a pressure of about 100 psi to about 15,000 psi.

20. The method of claim 18 , wherein the fluid comprises water or brine.

21. A degradable polymer composition comprising,

a polyurethane comprising ester groups in a backbone of the polyurethane and carboxylic acid groups attached to the backbone of the polyurethane; and

a filler comprising a fiber having an average length of about ⅛ inch to about 5 inches, or a combination of the fiber with a powder, the powder comprising particles having an average size of about 5 microns to about 500 microns or a combination of the powder,

wherein the powder comprises one or more of the following: sodium chloride; a dissolvable silicate; aluminum hydroxide oxide; adipic acid; or succinic acid, the dissolvable silicate comprising about 66 to about 80 wt % of SiO 2 , about 0 to about 35 of Na 2 O, 0 to about 35 wt % of K 2 O, 0 to about 20 wt % of CaO, and 0 to about 10 wt % of MgO, provided that the sum of the weights of Na 2 O and K 2 O is about 20 wt % to about 40 wt %, each based on the total weight of the dissolvable silicate, and

the fiber comprises glass fiber, and the glass fiber contains a dissolvable silicate comprising about 66 to about 80 wt. % of SiO 2 , about 0 to about 35 of Na 2 O, 0 to about 35 wt. % of K 2 O, 0 to about 20 wt. % of CaO, and 0 to about 10 wt. % of MgO, provided that the sum of the weights of Na 2 O and K 2 O is about 20 wt. % to about 40 wt. %, each based on the total weight of the dissolvable silicate.