IP Library › Granted Patent US 12,049,557
Granted Patent B2
US 12,049,557 · App. 17/369,571 · Granted Jul 30, 2024

Bi-continuos epoxy microstructure for fabrication of degradable thermoset composite used in HTHP downhole conditions

Inventors: Lei Zhao (Houston, IL); Jiaxiang (Jason) Ren (Houston, IL); Peng Cheng (Houston, TX); Huailiang Liu (Beijing, CN)
Assignees: CNPC USA CORP.; BEIJING HUAMEI, INC.; CHINA NATIONAL PETROLEUM CORPORATION
C08L63/00C08L2205/03C08L2205/16
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Quick Facts
Patent No.
US 12,049,557
App. No.
17/369,571
Granted
Jul 30, 2024
Kind
B2
Abstract

The patent application discloses a degradable thermoset composite. The composite comprises a reaction product of an epoxy resin mixture, a cross-linker, a catalyst. The epoxy resin mixture may comprise at least one aromatic epoxy resins having a glass transition temperature greater than or equal to 150° C. The reaction product may have a glass transition temperature greater than or equal to 110° C. as measured by DSC or DMA.

Claims (31)

1. A degradable thermoset composite, comprising a reaction product of:

an epoxy resin mixture, wherein the epoxy resin mixture comprises at least one aromatic epoxy resins having a glass transition temperature greater than or equal to about 150° C.;

a cross-linker; and

a catalyst for accelerating hydrolysis of the thermoset composite, wherein the catalyst comprises an inorganic material;

wherein the degradable thermoset composite has a glass transition temperature greater than or equal to about 110° C. as measured by DSC or DMA.

2. The degradable thermoset composite of claim 1 , wherein the reaction product has a tensile strength of at least about 10000 psi.

3. The degradable thermoset composite of claim 1 , wherein the catalyst comprises at least one of solid base or solid acid.

4. The degradable thermoset composite of claim 1 , wherein the epoxy resin mixture comprises at least one epoxy resins having a glass transition temperature lower than or equal to about 100° C.

5. The degradable thermoset composite of claim 1 , wherein the epoxy resin mixture further comprises a flexibilized epoxy resin.

6. The degradable thermoset composite of claim 1 , wherein the aromatic epoxy resin comprises at least one of an epoxy phenolic novolac resin, an epoxy bisphenol-A novolac resin, a multifunctional epoxy resin, or combination thereof.

7. The degradable thermoset composite of claim 1 , wherein the degradable thermoset composite degrades below about 100° C. under water or brine.

8. The degradable thermoset composite of claim 1 , wherein the aromatic epoxy resin comprises:

at least one of a bisphenol-A based epoxy resin, bisphenol-F based epoxy resin, Aromatic Glycidyl Amines, or Phenolic Novolacs, or combination thereof.

9. The degradable thermoset composite of claim 1 further comprises fibers, wherein fibers are at least one of glass fibers, carbon fibers, aramid fibers, wherein loadings of fibers are from about 20% to about 60% in volume.

10. The degradable thermoset composite of claim 1 , wherein the cross-linker comprises a cycloaliphatic anhydride.

11. A process for forming a degradable thermoset composition, the process comprising:

admixing a first epoxy resin and a second epoxy resin to form a mixture, wherein the first epoxy resin has a higher glass transition temperature than the second epoxy resin; and

adding a catalyst for accelerating hydrolysis of the thermoset composite, wherein the catalyst comprises an inorganic material, and a cross-linker to form a curable composition, wherein the first epoxy resin comprises at least one aromatic epoxy resin having a glass transition temperature greater than or equal to about 150° C.

12. The process of claim 11 , wherein the 2 nd epoxy resin further comprises a flexibilized epoxy resin.

13. The process of claim 11 , wherein the first epoxy resin further comprises an epoxy phenolic novolac resin, an epoxy bisphenol diglycidyl ether, a multifunctional epoxy resin or combination thereof.

14. The process of claim 11 , wherein the first epoxy resin further comprises at least one of a bisphenol-A based epoxy resin, polyglycidyl ethers of phenolic novolacs, polyglycidyl ethers of cresolic novolacs, or combination thereof.

15. The process of claim 11 , wherein the cross-linker comprises a cycloaliphatic anhydride.

16. The process of claim 11 , wherein the degradable thermoset composite degrades below about 100° C. under water or brine.

17. A degradable thermoset composite, comprising a reaction product of:

an epoxy resin mixture, wherein the epoxy resin mixture comprises at least a first epoxy resin and a second epoxy resin, wherein the first epoxy resin has a glass transition temperature greater than that of the second epoxy resin;

a cross-linker; and

a catalyst for accelerating hydrolysis of the thermoset composite, wherein the catalyst comprises an inorganic material.

18. The degradable thermoset composite of claim 17 , wherein the first epoxy resin further comprises:

at least one of a bisphenol-A based epoxy resin, bisphenol-F based epoxy resin, Aromatic Glycidyl Amines, or Phenolic Novolacs, or combination thereof.

19. The degradable thermoset composite of claim 17 , wherein the cross-linker comprises a cycloaliphatic anhydride.

20. The degradable thermoset composite of claim 17 , wherein the first epoxy resin comprises at least one of polyglycidyl ethers of phenolic novolacs, polyglycidyl ethers of cresolic novolacs, or combination thereof.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 4, 2023
From: LIU, HUAILIANG; CHENG, PENG
To: CNPC USA CORP.
Reel/Frame 063216/0134 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 4, 2023
From: CNPC USA CORP.
To: CNPC USA CORP.; BEIJING HUAMEI INC.; CHINA NATIONAL PETROLEUM CORPORATION
Reel/Frame 063216/0524 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 7, 2021
From: ZHAO, LEI; REN, JIAXIANG
To: CNPC USA CORPORATION
Reel/Frame 056780/0358 →
Continuity (1)
Related Publication 20230022703A1 · Jan 26, 2023